Personal care compositions

ABSTRACT

The present invention relates to personal care compositions comprising a copolymer complex and a volatile, hydrophobic solvent component for solubilizing or dispersing the copolymer complex. The copolymer complex is formed by complexing a fatty amine with a copolymer, wherein the copolymer comprises a hydrophobic monomer, a hydrophilic monomer such that at least 1%, by weight of the total copolymer, comprises hydrophilic monomers bearing acidic functional groups, and optionally a hydrophobic macromonomer.

This is a continuation-in-part of application Ser. No. 08/708,334, filedon Sep. 4, 1996 now abandoned.

TECHNICAL FIELD

The present invention relates to personal care compositions comprising acopolymer complex and a volatile, hydrophobic solvent component forsolubilizing or dispersing the copolymer complex. The copolymer complexis formed by complexing a fatty amine with a copolymer, wherein thecopolymer comprises a hydrophobic monomer, a hydrophilic monomer suchthat at least 1%, by weight of the total copolymer, compriseshydrophilic monomers bearing acidic functional groups, and optionally ahydrophobic macromonomer. These compositions provide improved delivery,deposition and retention to the hair and skin.

BACKGROUND OF THE INVENTION

The rheological, holding, and film-forming properties of polymers andcopolymers have contributed immensely to their usefulness in a widevariety of personal care compositions. Products containing polymersinclude hairsprays, shampoos, hair conditioners, skin creams andlotions, make-up products, antiperspirants and deodorants, shavingcreams, topical drug compositions, sunscreen products, and the like.Consumers are constantly seeking products providing improved performancebenefits.

In their quest to improve upon current products and to create newproducts, scientists and formulators are continually seeking to developnew key ingredients for such products. Because polymers play such animportant role in the formulation of many personal care products, a needexists for new polymers having new and useful properties. In the haircare area, for example, style retention is generally accomplished byapplication of either permanent chemical alteration products ortemporary styling products. A permanent chemical alteration product,which is commonly referred to as a "hair perm," typically involvestreating the hair with various sulfur-containing compounds in order tobreak the disulfide bonds in the hair fibers, thereby enabling one toalter the shape and orientation of the hair fibers. However, hair permproducts have the disadvantage of being harsh and damaging to the hair,and of being long-lasting and difficult to reverse. Conversely,temporary styling products generally do not break the chemical bonds inthe hair fibers. These temporary styling products typically are in theform of gels, lotions, mousses, or sprays containing polymeric resins orgums for coating the hair fibers and bonding them together. Manytemporary styling products are inconvenient to use and have thedisadvantage of not allowing one to readily restyle the hair after theinitial application and styling is completed, without furtherapplication of additional product. It would be preferable to deliverstyling and hold benefits using rinse-off products such as conditionersand shampoos. These types of rinse-off products, however, requirestyling agents that are substantive to the hair and not readily removedduring the rinsing process. Especially useful styling and hold agentsfor rinse-off compositions are hydrophobic polymeric materials. Suchhydrophobic materials, however, may cause a buildup of an unsightlyvisible residue on the hair with repeated usage. This residue caneventually completely surround the hair shaft and can be difficult toremove with normal shampooing. Therefore, the need exists for improvedcompositions for providing temporary styling and hold of human hairwithout the residue and negatives often associated with suchcompositions. Similarly, a need remains for film-forming skincompositions which are readily washed off by soap and water.

It has surprisingly been found that hair care products comprising acopolymer complex comprising a copolymer having at least one acidfunctional monomer and at least one fatty amine complexed with the acidfunctional monomer provide excellent temporary styling and hold benefitsin addition to improved "wash off" characteristics. The copolymercomplex of the present invention is soluble or dispersible in andreadily deposited by hydrophobic solvent components, yet easily washedaway by aqueous surfactant solutions. These compositions can be madeinto any of a number of conventional forms including, but not limitedto, shampoos, conditioners, mousses, gels, lotions, sprays and the like.

In addition to the afore-mentioned hair care benefits, it has been foundthat the copolymer complex and volatile, hydrophobic solvent componentof the present invention are also useful for incorporation into a widevariety of cosmetic and pharmaceutical compositions for topicalapplication to the skin. These materials provide topical compositionswhich are more easily and uniformly spread upon the skin, which feelgood upon the skin, and yet are highly substantive. Furthermore, thesecompositions are useful for providing occlusion to enhance thepenetration of a wide variety of cosmetic and pharmaceutical activesinto the skin, or alternatively, through the skin for systemic delivery.

The compositions of the present invention comprise a copolymer complexand a volatile, hydrophobic solvent component suitable for applicationto the hair or skin. The copolymer complex comprises a copolymer havingat least one acid functional monomer and at least one fatty aminecomplexed with the acid functional monomer.

It is therefore an object of the present invention to provide copolymercomplexes having improved solubility or dispersibility characteristics.

It is another object of the present invention to provide copolymercomplexes that are soluble or dispersible in hydrophobic solventcomponents and yet are readily washed away by aqueous surfactantsolutions.

It is another object of the present invention to provide personal carecompositions in the form of hair care compositions having improvedstyling and/or hold properties and having improved aesthetics.

It is another object of the present invention to provide personal carecompositions in the form of topical cosmetic and pharmaceuticalcompositions useful for delivering and retaining a wide variety ofcosmetic materials and pharmaceutical actives to and/or through theskin.

It is another object of the present invention to provide rinse offcompositions useful for styling and holding hair.

It is another object of the present invention to provide methods forstyling and holding the hair.

It is another object of the present invention to provide methods fordelivering and retaining to the skin cosmetic materials andpharmaceutical actives.

These and other objects will become readily apparent from the detaileddescription which follows.

SUMMARY OF THE INVENTION

The compositions of the present invention relate to personal carecompositions, comprising:

A.) a copolymer complex comprising:

a.) a copolymer having a backbone formed from the copolymerization ofrepeating A monomer and B monomer units wherein the backbone hasoptionally grafted to it hydrophobic C macromonomer units wherein thecopolymer is prepared by the polymerization combination of the followingrelative weight percentages of the A, B, and C units:

i) from about 10% to about 99% by weight of the copolymer of one or morehydrophobic A monomer units, wherein the A monomer units arecopolymerizble with the B monomer and C macromonomer units;

ii) from about 1% to about 40% by weight of the copolymer of one or morehydrophilic B monomer units, wherein the B monomer units arecopolymerizable with the A monomer and C macromonomer units and whereinat least about 1% by weight of the copolymer, of the B monomer units,are selected from B monomer units having at least one acid functionalgroup; and

iii) from 0 to about 50% by weight of the copolymer of one or more Cmacromonomer units wherein the C units are hydrophobic macromonomerunits, copolymerizable with the A monomer units and the B monomer units,the C macromonomer units having a number average molecular weight offrom about 1,500 to about 50,000; and

b.) a complexing fatty amine wherein the fatty amine forms a complexwith the acid functional group of the B monomer units;

wherein the weight ratio of the copolymer to the fatty amine is fromabout 50:1 to about 1:1; and

B.) a volatile, hydrophobic solvent component for the copolymer complexhaving a boiling point at 1 atmosphere of about 260° C. or less and asolubility parameter of about 8.5 (cal/cm³)^(1/2) or less

wherein the copolymer complex is soluble or dispersible in the volatile,hydrophobic solvent component.

In further embodiments, the present invention relates to a method ofmaking a personal care composition, comprising the steps of:

a.) preparing a copolymer having a backbone formed from thecopolymerization of repeating A monomer and B monomer units wherein thebackbone has optionally grafted to it hydrophobic C macromonomer unitswherein the copolymer is prepared by the polymerization combination ofthe following relative weight percentages of the A, B, and C units:

i) from about 10% to about 99% by weight of the copolymer of one or morehydrophobic A monomer units, wherein the A monomer units arecopolymerizable with the B monomer and C macromonomer units;

ii) from about 1% to about 40% by weight of the copolymer of one or morehydrophilic B monomer units, wherein the B monomer units arecopolymerizable with the A monomer and C macromonomer units and whereinat least about 1% by weight of the copolymer, of the B monomer units,are selected from B monomer units having at least one acid functionalgroup; and

iii) from 0 to about 50% by weight of the copolymer of one or more Cmacromonomer units wherein the C units are hydrophobic macromonomerunits, copolymerizable with the A monomer units and the B monomer units,the C macromonomer units having a number average molecular weight offrom about 1,500 to about 50,000; and

b.) complexing the copolymer with a fatty amine wherein the weight ratioof the copolymer to the fatty amine is from about 50:1 to about 1:1; and

c.) dissolving or dispersing the copolymer complex in a volatile,hydrophobic solvent component having a boiling point at 1 atmosphere ofabout 260° C. or less and a solubility parameter of about 8.5(cal/cm³)^(1/2) or less.

In further embodiments, the present invention relates to a personal carecomposition which or to mixing, comprises:

A.) a copolymer complex comprising:

a.) a copolymer having a backbone formed from the copolymerization ofrepeating A monomer and B monomer units wherein the backbone hasoptionally grafted to it hydrophobic C macromonomer units wherein thecopolymer is prepared by the polymerization combination of the followingrelative weight percentages of the A, B, and C units:

i) from about 10% to about 99% by weight of the copolymer of one or morehydrophobic A monomer units, wherein the A monomer units arecopolymerizable with the B monomer and C macromonomer units;

ii) from about 1% to about 40% by weight of the copolymer of one or morehydrophilic B monomer units, wherein the B monomer units arecopolymerizable with the A monomer and C macromonomer units and whereinat least about 1% by weight of the copolymer, of the B monomer units,are selected from B monomer units having at least one acid functionalgroup; and

iii) from 0 to about 50% by weight of the copolymer of one or more Cmacromonomer units wherein the C units are hydrophobic macromonomerunits, copolymerizable with the A monomer units and the B monomer units,the C macromonomer units having a number average molecular weight offrom about 1,500 to about 50,000; and

b.) a complexing fatty amine wherein the fatty amine forms a complexwith the acid functional B monomer units

wherein the weight ratio of the copolymer to the fatty amine is fromabout 50:1 to about 1:1; and

B.) a volatile, hydrophobic solvent component for the copolymer complexhaving a boiling point at 1 atmosphere of about 260° C. or less and asolubility parameter of about 8.5 (cal/cm³)^(1/2) or less

wherein the copolymer complex is soluble or dispersible in the volatile,hydrophobic solvent component.

Unless otherwise indicated, all percentages and ratios used herein areby weight of the total composition. All weight percentages, unlessotherwise indicated, are on an actives weight basis. All measurementsmade are at 25° C., unless otherwise designated. The invention hereofcan comprise, consist of, or consist essentially of, the essential aswell as optional ingredients and components described herein.

DETAILED DESCRIPTION OF THE INVENTION Essential Components

The compositions of the present invention comprise a copolymer complexand a volatile, hydrophobic solvent component suitable for applicationto the hair and skin, wherein the copolymer complex comprises acopolymer complexed with a fatty amine.

The copolymers of the present invention can include graft copolymers.The term "graft copolymers" is familiar to one of ordinary skill inpolymer science and is used herein to describe the copolymers whichresult by adding or "grafting" a polymeric chemical moiety (i.e."grafts") onto another polymeric moiety commonly referred to as the"backbone". The backbone typically has a higher molecular weight thanthe grafts. Thus, graft copolymers can be described as polymers havingpendant polymeric side chains, and as being formed from the "grafting"or incorporation of polymeric side chains onto or into a polymer. Thepolymer to which the grafts are incorporated can be homopolymers orcopolymers. The graft copolymers are derived from a variety of monomerunits.

The copolymers of the present invention can be prepared from thecopolymerization of monomer units and macromonomer units such that themacromonomer units are "grafted" or incorporated into the resultingcopolymer. The term "macromonomer" is a term familiar to one of ordinaryskill in polymer science, and is used to described a polymeric materialcontaining a polymerizable moiety. In other words, a macromonomer is amacromolecular monomer, which is essentially a high molecular weighttype of monomer building block unit which can be used in apolymerization reaction to form polymers with itself; with othermonomers, or with other macromonomers.

The term "hydrophilic" is used herein consistent with its standardmeaning of having affinity for water, whereas "hydrophobic" is usedherein consistent with its standard meaning of lacking affinity forwater. As used herein in relation to monomer units and polymericmaterials, including the macromonomers, copolymers, and solvents for thecopolymers, "hydrophilic" means substantially water soluble."Substantially water soluble" shall refer to a material that is solublein distilled (or equivalent) water, at 25° C., at a concentration of0.2% by weight, and are preferably soluble at 1.0% by weight Incontrast, "hydrophobic" means substantially water insoluble. In thisregard, "substantially water insoluble" shall refer to a material thatis not soluble in distilled (or equivalent) water, at 25° C., at aconcentration of 0.2% by weight, and preferably not soluble at 0.1% byweight.

The term "soluble" or "solubility" as used herein, means the capabilityof a substance to form a solution, i.e., either a true solution or acolloidal solution. A true solution being a uniformly dispersed mixtureat the molecular or ionic level, of one or more substances (the solute)in one or more substances (the solvent). These two parts of a solutionare called phases. A colloidal dispersion is often called a solution.Since colloidal particles are larger than molecules it is strictlyincorrect to call such dispersions solutions; however this term iswidely used in the literature. The term "dispersible" or"dispersibility" as used herein, means the capability of a substance toform a dispersion, i.e., a two-phase system where one phase consists offinely divided particles (often in the colloidal size range) distributedthroughout a bulk substance, the particles being the disperse orinternal phase and the bulk substance the continuous or external phase.

The term "rinse" off or wash off is used herein to mean that thecompositions of the present invention are used in a context whereby thecomposition is ultimately rinsed or washed from the hair and/or skineither after or during the application of the product Nonlimitingexamples of rinse-off products of the present invention include hairconditioners, shampoos and soaps.

The term "substantive" or "substantivity" as used herein, means thebinding or retention of a chemical or pharmaceutical active to thesurface layer of the stratum corneum or to hair.

The term "suitable for application to human hair and skin" as usedherein, means that the compositions or components thereof so describedare suitable for use in contact with human hair and the scalp and skinwithout undue toxicity, incompatibility, instability, allergic response,and the like.

The aforementioned definitions shall also apply to other materials sodescribed herein, to the extent any other definitions regarding suchmaterials are consistent with those stated above.

The compositions of the present invention comprise the followingessential components.

Copolymer complex

The hair and skin care compositions of the present invention comprisefrom about 0.25% to about 30%, preferably from about 2% to about 15%,and more preferably from about 2% to about 10%, by weight, based on theweight of the hair and skin care composition, of a copolymer complex.The copolymer complex comprises a copolymer having at least one acidfunctionalized monomer complexed with a fatty amine.

Copolymer

The copolymer complex of the present invention comprises from about 35%to about 99%, preferably from about 40% to about 90%, and morepreferably from about 50% to about 70%, by weight, based on the weightof copolymer complex, of a copolymer. Based on the weight of the overallhair and skin care composition, the copolymer comprises from about 0.1%to about 10%, preferably from about 1% to about 5%, and more preferablyfrom about 1.5% to about 3.5%, by weight.

The copolymers of the present invention have a weight average molecularweight, in grams/mole, of at least about 10,000. There is no upper limitfor molecular weight except that which limits applicability of theinvention for practical reasons, such as viscosity, processing,aesthetic characteristics, formulation compatibility, etc. The weightaverage molecular weight is generally less than about 5,000,000, moregenerally less than about 2,500,000, and typically less than about1,500,000. Preferably, the weight average molecular weight is from about10,000 to about 5,000,000, more preferably from about 50,000 to about2,000,000, even more preferably from about 75,000 to about 1,000,000,and most preferably from about 75,000 to about 500,000.

The copolymers of the present invention are formed from thecopolymerization of randomly repeating A monomer units and B monomerunits, preferably wherein the A monomers are polymerizable,ethylenically unsaturated monomers selected to meet the requirements ofthe copolymer. By "polymerizable," as used herein, is meant monomersthat can be polymerized using any conventional synthetic techniques.Monomers that are polymerizable using conventional free radicalinitiated techniques are preferred. The term "ethylenically unsaturated"is used herein to mean monomers that contain at least one polymerizablecarbon-carbon double bond (which can be mono-, di-, tri-, ortetra-substituted). The B monomer units are hydrophilic monomers whichare copolymerizable with A and selected from polar monomers, preferablyhaving a Tg or a Tm above about -20° C., and wherein at least 1%, byweight of the copolymer, of the hydrophilic B monomer is selected fromhydrophilic B monomers having at least one acid functional group. The Amonomer and B monomer units form what is termed the backbone of thepolymer and can be selected from a wide variety of structures as long asthe copolymer has the required properties and meets the molecular weightand other requirements described herein. The copolymers of the presentinvention may optionally incorporate C macromonomer units. The Cmacromonomer units are selected from at least one hydrophobicmacromonomer unit which contains a polymeric portion and a moietycopolymerizable with the A monomer and the B monomer. The C macromonomerunits form hydrophobic side chains on the copolymer.

The copolymers are prepared by the polymerization combination of A and Bmonomers and can be characterized by the weight percent of the monomerscharged to the reaction vessel in which the polymerization reaction isrun. C macromonomers may be optionally incorporated into thepolymerization reaction.

As will be clear to one skilled in the art and especially from theExamples, the copolymer may have one or more hydrophobic side chainsgrafted to the backbone. As known in the art, synthetic graftcopolymerization processes may produce a mixture of polymer moleculescontaining no, one, or more than one hydrophobic side chains covalentlybonded to and pendant from the polymeric backbone. From knowledge of theamount and number average molecular weight of hydrophobic side chains ina polymer sample, and the number average molecular weight of the polymersample, it is possible to calculate the average number of hydrophobicside chains per polymer backbone.

The copolymer complex of the present invention, when dried to a filmhaving 0.5% or less of the volatile hydrophobic solvent component, havea Tg or Tm of at least about -20° C., more preferably at least about 20°C., so that the copolymers are not unduly sticky, or "tacky" to thetouch. As used herein, the abbreviation "Tg" refers to the glasstransition temperature of the backbone of the polymer, and theabbreviation "Tm" refers to the crystalline melting point of thebackbone, if such a transition exists for a given polymer. Preferably,both the Tg and the Tm, if any, are above about -20° C., more preferablyabove about 20° C.

The grafted copolymers should satisfy the following criteria:

(1) the polymeric side chain portion is covalently bonded to thebackbone portion; and

(2) the number average molecular weight of the polymeric side chainportion is from about 1,500 to about 50,000.

The copolymers of the present invention are prepared by thepolymerization combination of A monomers and B monomers. C macromonomersmay optionally be incorporated into the polymerization process. Thecopolymers can be synthesized by free radical polymerization of themonomers and macromonomers. The general principles of free radicalpolymerization methods are well understood. See for example, Odian,"Principles of Polymerization", 3rd edition, John Wiley & Sons, 1991,pp. 198-334. The desired monomers and macromonomers are all placed in areactor, along with a sufficient amount of a mutual solvent so that whenthe reaction is complete the viscosity of the reaction is reasonable.Undesired terminators, especially oxygen, are removed as needed. This isdone by evacuation or by purging with an inert gas, such as argon ornitrogen. The initiator is introduced and the reaction brought to thetemperature needed for initiation to occur, assuming thermal initiatorsare used. Alternatively, redox or radiation initiation can be used. Thepolymerization is allowed to proceed as long as needed for a high levelof conversion to be achieved, typically from a few hours to a few days.The solvent is then removed, usually by evaporation or by precipitatingthe copolymer by addition of a nonsolvent The copolymer can be furtherpurified, as desired.

As an alternative to a batch reaction, the copolymer can be made by asemi-continuous or continuous process. In the semi-continuous process,two or more additions of monomers or macromonomers are made during thepolymerization reaction. This is advantageous when the copolymer is madeof several monomers which react during the polymerization at differentrates. The proportions of monomers added to the reaction at the separatepoints of addition can be adjusted by one of ordinary skill in the artsuch that the polymers of the final product have a more uniformstructure. In other words, the polymers of the final product will have amore consistent monomer content distribution for each of the monomertypes charged to the reaction.

Examples of related copolymers and how they are made are described indetail in U.S. Pat. No. 4,693,935, Mazurek, issued Sep. 15, 1987, U.S.Pat. No. 4,728,571, Clemens et al., issued Mar. 1, 1988, both of whichare incorporated herein by reference. Additional grafted polymers arealso disclosed in U.S. Pat. Nos. 5,166,276 and 5,480,634, Hayama, etal., issued Nov. 24, 1992 and Jan. 2, 1996, respectively, U.S. Pat. No.5,061,481, Suzuli et al., issued Oct. 29, 1991; U.S. Pat. No. 5,106,609,Bolich et al., issued Apr. 21, 1992; U.S. Pat. No. 5,100,658, Bolich etal., issued Mar. 31, 1992; U.S. Pat. No. 5,100,657, Ansher-Jackson, etal., issued Mar. 31, 1992; and U.S. Pat. No. 5,104,646, Bolich et al.,issued Apr. 14, 1992, all of which are incorporated by reference hereinin their entirety.

The copolymer composition is characterized by the amount of each monomercharged to the polymerization reaction vessel, or alternatively used ina continuous or semi-continuous process.

By appropriate selection and combination of the particular monomer unitsand macromonomer units, and by the choice of specific relative ratios ofthe units well within the ability of one of ordinary skill in the art,the copolymers can be optimized for various physical properties and forcompatibility with other ingredients commonly used in hair careapplications.

A Monomer Units

The copolymers of the present invention comprise from about 10% to about99%, preferably from about 40% to about 80%, and more preferably fromabout 50% to about 70%, by weight of the hydrophobic copolymer, of Amonomer units.

The A monomer unit is selected from copolymerizable hydrophobic monomersor mixtures thereof, preferably ethylenically unsaturated monomers.Either a single type of A monomer unit or combinations of two or more Amonomer units can be utilized. The A monomers are selected to meet therequirements of the copolymer. Preferably, the A units are soluble ordispersible in the volatile, hydrophobic solvent component. By"copolymerizable", as used herein, is meant that the A monomer can bereacted with or polymerized with the B monomers or C macromonomers in apolymerization reaction using one or more conventional synthetictechniques, such as ionic, emulsion, dispersion, Ziegler-Natta, freeradical, group transfer or step growth polymerization. In the presentinvention, monomers and macromonomers that are copolymerizable usingconventional free radical initiated techniques are preferred. The term"ethylenically unsaturated" is used herein to mean a material thatcontains at least one polymerizable carbon-carbon double bond, which canbe mono-, di-, tri- or tetra-substituted.

Nonlimiting classes of A hydrophobic monomers useful herein includemonomers selected from the group consisting of unsaturated carboxylicacid esters of C1-C18 alcohols, unsaturated alcohols (preferably havingabout 12 to about 30 carbons), unsaturated hydrocarbons, aromatichydrocarbons containing unsaturated alkyl groups, vinyl esters ofcarboxylic acids, vinyl ethers, allyl esters of carboyxlic acids, allylethers, and mixtures thereof.

Representative examples of hydrophobic monomers include acrylic ormethacrylic acid esters of C₁ -C₁₈ alcohols such as methanol, ethanolmethoxy ethanol, 1-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol,1-decanol, 2-ethylhexanol, cyclohexanol, and the like; dicyclopentenylacrylate; 4-biphenyl acrylate, pentachlorophenyl acrylate;3,5-dimethyladamantyl acrylate; 4-methoxycarbonylphenyl methacrylate,trimethylsilyl methacrylate; styrenes such as methyl styrene; t-butylstyrene, isopropyl sytrene; vinyl esters, such as vinyl acetate, vinylneononanoate, vinyl pivalate; and vinyl propionate; vinyl chloride;vinyl toluene; allyl vinyl ethers, including isobutyl vinyl ether ands-butyl vinyl ether; allyl chloride, allyl acetate, 1,2-butadiene;1,3-buatdiene, 1,3-hexadiene, 1,3-cyclohexadiene; bicycloheptadiene;2,3-dicarboxylmethyl-1,6-hexadiene; ethylene; propylene; isoprene;1-butene, 2-butene, isobutylene, indene; norbornylene; β-pinene;α-pinene; and mixtures thereof.

Preferred hydrophobic monomers suitable for use as the A monomer unitsinclude monomers selected from the group consisting of n-butylmethacrylate, isobutyl methacrylate, t-butyl acrylate, t-butylmethacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, t-butylstyrene and mixtures thereof. More preferred are monomer units selectedfrom the group consisting of t-butyl styrene, t-butyl acrylate, t-butylmethacrylate, 2-ethylhexyl methacrylate and mixtures thereof.

B Monomer Units

The copolymers of the present invention comprise from about 1% to about40%, preferably from about 5% to about 30%, and more preferably fromabout 10% to about 25%, by weight of the copolymer, of B monomer units.

The B monomer unit is selected from hydrophilic, copolymerizablemonomers, preferably ethylenically unsaturated monomers, comprising atleast one monomer copolymerizable with the A monomer unit. Either asingle type of B monomer unit or combinations of two or more B monomerunits can be utilized. The B monomers are selected to meet therequirements of the copolymer. By "copolymerizable", as used herein, ismeant that the B monomer can be reacted with or polymerized with the Amonomers or C macromonomers in a polymerization reaction using one ormore conventional synthetic techniques, such as ionic, emulsion,dispersion, Ziegler-Natta, free radical, group transfer or step growthpolymerization. In the present invention, monomers and macromonomersthat are copolymerizable using conventional free radical initiatedtechniques are preferred. The term "ethylenically unsaturated" is usedherein to mean a material that contains at least one polymerizablecarbon-carbon double bond, which can be mono-, di-, tri- ortetra-substituted. The B monomer units are selected from hydrophilicmonomers wherein at least 1% by weight based on the weight of thecopolymer, of the copolymer, comprises hydrophilic monomers having atleast one acid functional group. The hydrophilic monomers preferably areselected such that a polymer of these monomers has a Tg or a Tm aboveabout -20° C.

Preferred hydrophilic B monomers are copolymerizable with the A and Cmonomers, and are selected from the group consisting of unsaturatedorganic mono- and poly- carboxylic acids, unsaturated (meth)acrylates,unsaturated (meth)acrylamides, unsaturated (meth)acrylate alcohols,unsaturated aminoalkylacrylates, unsaturated organic acid anhydrides,unsaturated esters of organic acid anhydrides, hydrophilic unsaturatedvinyl compounds, hydrophilic unsaturated allyl compounds, hydrophilicunsaturated imides, salts of the foregoing compounds, and mixturesthereof.

Representative examples of B monomers include acid functional compoundssuch as acrylic acid, methacrylic acid, maleic acid, crotonic acid anditaconic acid as well as non-acid functional compounds such asN,N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternizeddimethylaminoethyl methacrylate, methacrylamide, N-t-butyl acrylamide,maleic anhydride and its half esters, acrylamide, hydroxyethylmethacrylate, diallyldimethyl ammonium chloride, vinyl pyrrolidone,vinyl ethers (such as methyl vinyl ether), maleimides, vinyl pyridine,vinyl imidazole, other polar vinyl heterocyclics, styrene sulfonate,allyl alcohol, vinyl alcohol (produced by the hydrolysis of vinylacetate after polymerization) and mixtures thereof. More preferred are Bmonomers selected from the group consisting of acrylic acid, methacrylicacid, N,N-dimethyl-acrylamide, dimethylaminoethyl methacrylate, vinylpyrrolidone, and mixtures thereof. It is remains critical, however, thatat least 1% by weight, based on the weight of the copolymer, comprises Bmonomers having at least one acid functional group.

C Macromonomer Units

The copolymers of the present invention can comprise from about 0% toabout 50%, preferably from about 5% to about 40%, and more preferablyfrom about 15% to about 30%, by weight of the copolymer of Cmacromonomer units.

The C macromonomer units are hydrophobic macromonomers copolymerizablewith the A and B monomers, said C macromonomers preferably having anethylenically unsaturated moiety. Either a single type of C macromonomerunit or combinations or two or more C macromonomer units can be utilizedherein. The C macromonomers are selected to meet the requirements of thecopolymer. By "copolymerizable", as used herein, is meant that the Cmacromonomers can be reacted with or polymerized with the A and Bmonomers in a polymerization reaction using one or more conventionalsynthetic techniques, as described above.

C macromonomers that are useful herein contain a polymeric portion and acopolyermizable moiety which is preferably an ethylenically unsaturatedmoiety. Typically, the preferred C macromonomers are those that areendcapped with the ethylenically unsaturated moiety. By "endcapped" asused herein is meant that the ethylenically unsaturated moiety is at ornear a terminal position of the macromonomer.

The C macromonomers can be synthesized utilizing a variety of standardsynthetic procedures familiar to the polymer chemist of ordinary skillin the art. Furthermore, these macromonomers can be synthesized startingfrom commercially available polymers. The C macromonomer has a numberaverage molecular weight from about 1500 to about 50,000, preferablyfrom about 5000 to about 50,000, more preferably from about 5,000 toabout 30,000, and most preferably from about 8,000 to about 25,000.

Preferably, the C macromonomer units are selected from the groupconsisting of polysiloxane macromonomers, polyalkylene macromonomers,and mixtures thereof.

Polysiloxane C macromonomers are exemplified by the general formula:

    X(Y).sub.n Si(R).sub.3-m Z.sub.m

wherein X is an ethylenically unsaturated group copolymerizable with theA monomers, such as a vinyl group; Y is a divalent liking group; R is ahydrogen, hydroxyl, lower alkyl (e.g. C₁ -C₄), phenyl, C₁ -C₄allyl-substituted aryl, C₁ -C₄ alkoxy, or C₁ -C₄ alkyl or dialkylamino;Z is a monovalent siloxane polymeric moiety having a number averagemolecular weight of at least about 1500, is essentially unreactive undercopolymerization conditions, and is pendant from the vinyl polymericbackbone described above; n is 0 or 1; and m is an integer from 1 to 3.

Preferably, the C macromonomer has a formula selected from the followingformulas: ##STR1## In these structures s is an integer from 0 to 6,preferably 0, 1, or 2, more preferably 0 or 1; m is an integer from 1 to3, preferably 1; p is 0 or 1; q is an integer from 2 to 6; R² isselected from the group consisting of C₁ -C₁₀ alkyl or C₁ -C₄alkyl-substituted aryl, preferably C₁ -C₆ alkyl or C₁ -C₄alkyl-substituted aryl, more preferably C₁ -C₂ alkyl; n is an integerselected from 0 to 4, preferably 0 or 1, more preferably 0; R¹ ishydrogen, hydroxyl, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkyl amino ordialkylamino, phenyl, C₁ -C₄ alkyl substituted aryl, preferably R¹ is C₁-C₄ alkyl; X is ##STR2## R³ is hydrogen or --COOH, preferably R³ ishydrogen; R⁴ is hydrogen, methyl or --CH₂ COOH, preferably R⁴ is methyl;Z is ##STR3## R⁵, R⁶, and R⁷, independently are C₁ -C₄ alkyl, C₁ -C₄alkoxy, C₁ -C₄ alkyl or dialkylamino, phenyl, C₁ -C₄ allyl-substitutedaryl, hydrogen or hydroxyl, preferably R⁵, R⁶, and R⁷ are C₁ -C₄ alkyl;and r is an integer of from about 20 to about 900, preferably about 20to about 675, more preferably r is from about 100 to about 325. Mostpreferably, R⁵, R⁶, and R⁷ are methyl, p=0, and q=3.

Polyalkylene macromonomers are exemplified by the general formula:

     I!.sub.n - W!.sub.m -E

wherein I is an optionally present initiator (i.e. n=0 or 1), W is ahydrophobic monomer unit, E is an endcapping group, and m is an integerfrom about 10 to about 2000.

I is an optionally present chemical initiator moiety. Without beinglimited by theory, I can be derived from a chemical initiator or solventused in the synthesis of the C macromonomer. Nonlimiting examples ofsuch initiators from which I can be derived include hydrogen ion,hydrogen radical, hydride ion, hydroxide ion, hydroxyl radical, peroxideradical, peroxide anion, C1-C20 carbocations, C1-C20 carbanions, C1-C20carbon radicals, C1-C20 aliphatic and aromatic alkoxy anions, ammoniumion, and substituted ammonium ions (e.g., C1-C20 alkyl and C1-C20 alkoxysubstituted), and mixtures thereof. I can be derived from any usefulsolvent, nonlimiting examples of which include water, methanol, ethanol,propanol, isopropanol, acetone, hexane, dichloromethane, chloroform,benzene, toluene, and mixtures thereof.

W is selected from one or more hydrophobic monomer units. Nonlimitingclasses of such monomers include C1-C18 acrylate esters, C1-C18(alk)acrylate esters, C2-C30 straight and branched chain alkenes,styrenes, C1-C30 vinyl ethers, C4-C30 straight and branched chaindienes, and mixtures thereof.

Nonlimiting examples of W groups include those selected from the groupconsisting of n-butyl acrylate, dodecyl acrylate, ethyl acrylate,2-ethybutyl acrylate, n-heptyl acrylate, n-hexylacrylate, iso-butylacrylate, iso-decyl acrylate, iso-propyl acrylate, 3-methylbutylacrylate, 2-methylpentyl acrylate, nonyl acrylate, octyl acrylate,1-propyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate,n-dodecyl methacrylate, n-octadecyl methacrylate, n-decyl methacrylate,n-pentyl methacrylate, isobutylene, isoprene, 1,2-butadiene,1,3-butadiene, 5-methyl-1-hexene, 6-methyl-1-heptene,4,4-dimethyl-1-pentene, iso-butyl vinyl ether, styrene, 2-methylstyrene, 3-methylstyrene, 4-methyl styrene, 2-t-butyl styrene, 3-t-butylstyrene, 4-t-butyl styrene, and mixtures thereof.

E is a copolymerizable moiety or "endcapping" group. Preferably E is anethylenically unsaturated moiety. More preferred is when E is selectedfrom the group consisting of vinyl, allyl, acryloyl, methacryloyl,ethacryloyl, 2-vinylbenzyl, 3-vinylbenzyl, 4-vinylbenzyl,2-vinylbenzoyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl, 1-propenyl,isobutenyl, cyclohexenyl, cyclopentenyl, and mixtures thereof. Even morepreferred is when E is selected from the group consisting of vinyl,allyl, acryloyl, methacryloyl, ethacryloyl, 3-vinylbenzyl,4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl, 1-propenyl,isobutenyl, and mixtures thereof. Most preferred is when E is selectedfrom the group consisting of vinyl, allyl, acryloyl, methacryloyl,ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, and mixtures thereof.

Nonlimiting examples of polysiloxane and polyalkylene C macromonomerunits useful herein include those selected from the group consisting ofacryloyl, methacryloyl, or 3-, or 4-vinylbenzyl endcapped polymers ofpolydimethylsiloxane, polydiethylsiloxane, polyphenylmethylsiloxane,polyphenylethylsiloxane, poly(n-butyl acrylate), poly(dodecyl acrylate),poly(2-ethylhexyl acrylate), poly(2-ethylbutyl acrylate), poly(ethylacrylate), poly(n-heptyl acrylate), poly(n-hexyl acrylate),poly(iso-butyl acrylate), poly(iso-decyl acrylate, poly(iso-propylacrylate), poly(3-methylbutyl acrylate), poly(2-methylpentyl acrylate),poly(nonyl acrylate), poly(octyl acrylate), poly(propyl acrylate), poly(2-ethylhexyl methacrylate), poly(tridecyl methacrylate), poly (hexylmethacrylate), poly(decyl methacrylate), poly(octyl methacrylate),poly(octadecyl methacrylate), poly(dodecyl methacrylate), poly(n-pentylmethacrylate), poly(isobutylene), poly(isoprene), hydrogenatedpoly(1,2-butadiene), hydrogenated poly(1,4-butadiene), hydrogenatedpoly(isoprene), poly(1,2-butadiene), poly(1-butene),poly(5-methyl-1-hexene), poly(6-methyl-1-heptene),poly(4,4-dimethyl-1-pentene), poly(iso-butyl vinyl ether), poly 4t-butylvinyl benzene-co-2-ethylhexyl acrylate!, poly 2-ethylhexylacrylate-co-octyl acrylamide), poly 2-ethyl vinylbenzene-co-octyl-methacrylate)!, and mixtures thereof.

"Copolymer" type C macromonomers containing two or more differentrandomly repeating monomer units are useful herein. Nonlimiting examplesof these "copolymer type of macromonomers include acryloyl endcappedpoly co(4-t-butyl vinyl benzene)(2,4-dimethyl vinyl benzene)!, polyco(4-t-butyl vinyl benzene)(2-ethylhexyl acrylate)!, polyco(2,4-dimethyl vinyl benzene)(2-ethylhexyl acrylate)!, poly co(2-ethylvinyl benzene)(octylmethacrylate)!, and the like.

Nonlimiting Examples of Polymers of the Present Invention

Nonlimiting examples of polymers useful for making the complexes of thepresent invention include those selected from the group consisting ofpoly (t-butylacrylate-co-acrylic acid)-graft-poly(dimethylsiloxane)!,poly (4-t-butylstyrene-co-acrylic acid)-graft-poly(dimethylsiloxane)!,poly t-butylacrylate-co-acrylic acid)-graft-poly(isobutylene)!, poly(4-t-butylstyrene-co-acrylic acid)-graft-poly(isobutylene)!, poly(t-butylstyrene-co-acrylic acid)-graft-poly(2-ethylhexyl methacrylate)!,poly (4-t-butylacrylate-co-styrene-co-acrylicacid)-graft-poly(isobutylene)!, poly (t-butylacrylate-co-methacrylicacid)-graft-poly(dimethylsiloxane)!, poly(4-t-butylstyrene-co-methacrylic acid)-graft-poly(dimethylsiloxane)!,poly t-butylacrylate-co-methacrylic acid)-graft-poly(isobutylene)!, poly(4-t-butylstyrene-co-methacrylic acid)-graft-poly(isobutylene)!, poly(t-butylstyrene-co-methacrylic acid)-graft-poly(2-ethylhexylmethacrylate)!, poly (4-t-butylacrylate-co-styrene-co-methacrylicacid)-graft-poly(isobutylene)!, and mixtures thereof.

The following more specific nonlimiting examples of polymers useful formaking the complexes of the compositions of the present inventioninclude the following. The weight percents refer to the amount ofmonomer and macromonomer reactants added in the polymerization reaction,not necessarily the amount in the finished polymer.

(I) a copolymer prepared from the polymerization reaction of 10 weightpercent acrylic acid, 70 weight percent isobutylmethacrylate and 20weight percent polydimethylsiloxane macromonomer having a weight averagemolecular weight of about 20,000.

(II) a copolymer prepared from the polymerization reaction of 20 weightpercent acrylic acid, 62 weight percent t-butyl acrylate and 18 weightpercent polydimethylsiloxane macromonomer having a weight averagemolecular weight of about 15,000.

(III) a copolymer prepared from the polymerization reaction of 50 weightpercent t-butylacrylate, 10 weight percent t-butyl methacrylate, 10weight percent acrylic acid, 10 weight percent ethylhexyl methacrylateand 20 weight percent polydimethylsiloxane macromonomer having a weightaverage molecular weight of about 10,000.

(IV) a copolymer prepared from the polymerization reaction of 60 weightpercent t-butylacrylate, 15 weight percent acrylic acid, 10 weightpercent ethylhexyl methacrylate and 15 weight percentpolydimethylsiloxane macromonomer having a weight average molecularweight of about 10,000.

(V) a copolymer prepared from the polymerization reaction of 70 weightpercent t-butylacrylate, 10 weight percent methacrylic acid, and 20weight percent polyisobutylene macromonomer having a weight averagemolecular weight of about 10,000.

(VI) a copolymer prepared from the polymerization reaction of 75 weightpercent t-butylacrylate, 5 weight percent acrylic acid, and 20 weightpercent polydimethylsiloxane macromonomer having a weight averagemolecular weight of about 10,000.

(VI) a copolymer prepared from the polymerization reaction of 70 weightpercent t-butylacrylate, 10 weight percent acrylic acid, and 20 weightpercent ethylhexyl methacrylate.

(VII) poly (t-butyl acrylate-co-acrylicacid)-graft-polydimethylsiloxane)! having a weight average molecularweight of about 700,000, comprising about 67% t-butyl acrylate, about 3%acrylic acid, and about 30% dimethylsiloxane macromonomer with a weightaverage molecular weight of about 11,000.

Fatty Amine

The copolymer component of the present invention comprises from about 1%to about 65%, preferably from about 10% to about 60%, and morepreferably from about 30% to about 50%, based on the weight of thecopolymer complex, of a complexing, fatty amine and derivatives thereofand salts thereof.

Fatty amines useful to compositions of the present invention includeprimary, secondary and tertiary amines, quaternary ammonium salts, alkylsubstituted heterocyclic amines, and polyamines such as diamines andtriamines. Also useful herein are salts of these amines and quaternizedderivatives of these amines.

It is critical to the present invention that copolymer complex formed bythe acid functional monomer and the complexing amine be soluble ordispersible in the volatile, hydrophobic solvent component discussedbelow. Without being limited by theory, it is believed that the fattyamines associate with the acid functional monomers of the copolymerbackbone so as to shield the hydrophilic, acid functional group from thehydrophobic solvent, improving the stability of the solubilized and/ordispersed copolymer complex

Primary amines or salts thereof having the formula R¹ --NH₂ wherein R¹is a C₁ -C₂₂ straight or branched chain aliphatic, hydroxyalkyl,amidoalkyl, carboxyalkyl, cyclic, alkoxy, polyalkoxy, orhydroxypolyalkoxy group function as useful fatty amines.

Secondary amines or salts thereof having the formula R¹ R² --NH whereinR¹ and R² are independently a C₁ -C₂₂ straight or branched chainaliphatic, hydroxyalkyl, amidoalkyl, carboxyalkyl, cyclic, alkoxy,polyalkoxy, or hydroxypolyalkoxy group also function as useful fattyamines.

Additionally, tertiary amines or salts thereof having the formula R¹ R²R³ N wherein R¹, R² and R³ are independently a C₁ -C₂₂ straight orbranched chain aliphatic, hydroxyalkyl, amidoalkyl, carboxyalkyl,cyclic, alkoxy, polyalkoxy, or hydroxypolyalkoxy group function well asfatty amines.

Other preferred complexing amines are quaternary ammonium compoundshaving the formula R¹ R² R³ R⁴ N⁺ X⁻ ! wherein R¹, R² ₁ R³ and R⁴ areindependently a C₁ -C₂₂ straight or branched chain aliphatic,hydroxyalkyl, amidoalkyl, carboxyalkyl, cyclic, alkoxy, polyalkoxy, orhydroxypolyalkoxy group and X is an anion. Examples of quaternaryammonium complexing amines include C₁₂ -C₁₈ alkyl dimethylammoniumchloride, octadecyltrimethylammonium chloride, cetyltrimethylammoniumbromide, n-dodecyltrimethylammonium hydroxide, tallow trimonium chlorideand n-octadecyltri-n-butylammonium nitrate.

Polyamines or salts thereof are also suitable for use in the presentinvention. Suitable polyamines are those having the formula R¹ R²--N((CH₃)_(x) N)_(n) --R¹ R² wherein R¹ and R² are independently ahydrogen atom or a C₁ -C₂₂ straight or branched chain aliphatic,hydroxyalkyl, amidoalkyl, carboxyalkyl, cyclic, alkoxy, polyalkoxy orhydroxypolyalkoxy group, x is an integer of 1 to 3, and n is an integerfrom 1 to 5. Representative polyamines are ethylenediamine,diethylenetriamine triethylenetetraamine, tetraethylenepentamine,pentaethylenehexamine, tallow propylenediamine, 1,2-propanediamine,1,3,5-pentanetriamine, and ethylenediaminetetraacetic acid (EDTA).

Heterocyclic amines or salts thereof having C₁ -C₂₂ straight or branchedchain allyl substituted imidazolines, morpholines, or piperidines arealso useful in the present invention. Typical heterocyclic aminesinclude aminoethyl hexadecylimidazoline, N-ethyl morpholine, and N-ethylpiperidine.

Mixtures of the above fatty amines may also be used. Preferred for usein forming the copolymer complexes of the present invention are tertiaryamines or salts thereof.

The copolymers of the present invention can be complexed with the fattyamines either during the polymerization process or after thepolymerization process as part of a final complexing step preferably ata weight ratio of copolymer to fatty amine of from about 50:1 to about1:1, more preferably from about 3:1 to about 10:7, more preferably fromabout 15:7 to about 10:7.

Volatile, Hydrophobic Solvent component

The compositions of the present invention further comprises from about1% to about 99.75%, preferably from about 4% to about 50%, and morepreferably from about 4% to about 20%, based on the weight of thecomposition, of a volatile, hydrophobic solvent for the copolymercomplex.

The term "solvent", as used herein, means a liquid suitable forsolubilizing or dispersing one or more of a variety of substances. Theterm "solvent component" as used herein means a liquid comprised of asingle solvent or a mixture of solvents. The term "volatile", as usedherein, means that the solvent exhibits a significant vapor pressure atambient conditions (e.g., 1 atmosphere at 25° C.), as understood bythose skilled in the scientific arts. Specially, the solvent componenthas a boiling point at one atmosphere of about 260° C. or less,preferably about 230° C. or less, more preferably about 215° C. or less,and most preferably about 210° C. or less and a solubility parameter ofabout 8.5 (cal/cm³)^(1/2) or less. In addition, the boiling point of thesolvent will generally be at least about 50° C., preferably at leastabout 90° C. The solvent component should also be acceptable for topicalapplication to the hair and the skin. The copolymers composed of themonomer and/or macromer units of the present invention must be solubleor dispersible in the volatile, hydrophobic solvent component oncecomplexed with the fatty amine complexing agent of the presentinvention.

Hydrophobic solvents suitable for use in the volatile, hydrophobicsolvent component are selected from the group consisting of branchedchain hydrocarbons, silicones, and mixtures thereof.

Preferred hydrophobic branched chain hydrocarbons useful as the solventcomponent herein contain from about 7 to about 14, more preferably fromabout 10 to about 13, and most preferably from about 11 to about 12carbon atoms. Saturated hydrocarbons are preferred, although it is notintended to exclude unsaturated hydrocarbons. Examples of such preferredbranched chain hydrocarbons include isoparaffins of the above chainsizes. Isoparaffins are commercially available form Exxon Chemical Co;examples include Isopar E (C₈ -C₉ isoparaffins), Isopar™ H and K (C₁₁-C₁₂ isoparaffins), and Isopar™ L (C₁₁ -C₁₃ isoparaffins) or mixturesthereof. Other suitable branched chain hydrocarbons are isododecane andisoundecane. Isododecane is preferred and is commercially available fromPresperse, Inc. (South Plainfield, N.J., USA) as Permethyl™ 99A.

Preferred silicones useful as the volatile hydrophobic solvent componentinclude volatile siloxanes such as phenyl pentamethyl disiloxane,phenylethylpentamethyl disiloxane, hexamethyl disiloxane, methoxypropylheptamethyl cyclotetrasiloxane, chloropropyl pentamethyldisiloxane, hydroxypropyl pentamethyl disiloxane, octamethylcyclotetrasiloxane, decamethyl cyclopentasiloxane, and mixtures thereof.More preferred among the silicones are cyclomethicones, examples ofwhich include hexamethyl disiloxane, octamethyl cyclo tetrasiloxane anddecamethyl cyclopentasiloxane, which are commonly referred to D4 and D5cyclomethicone, respectively.

Small amounts of hydrophilic solvents such as water, the C₁ -C₆alcohols, or mixtures thereof may also be incorporated herein so long asthe solubility parameter of the volatile, hydrophobic solvent componentis about 8.5 (cal/cm³)^(1/2) or less.

The copolymer complexes of the present invention are soluble ordispensable in the volatile, hydrophobic solvent component at aconcentration by weight of about 0.2%, preferably of about 0.5%, andmore preferably of about 1%.

In the case of the improved hair styling embodiments, the copolymercomplex and the volatile, hydrophobic solvent are preferably mixed suchthat the copolymer complex/solvent mixture has a viscosity above about5,000 cps, preferably from about 7,000 cps to about 250,000 cps and morepreferably from about 7,000 cps to about 15,000 cps. All viscosities aremeasured at 25° C. and at a shear rate of 10 sec⁻¹ using a Bohlin coneand plate viscometer Model VOR (cone diameter: 30 mm; cone angle: 2.5°)and are expressed in centipoise. Without being limited by theory, it isbelieved that these higher viscosity embodiments improve polymerdeposition efficiency and/or improve the weld morphology of polymerdroplets leading to improved hair style and hold.

Carriers

Hair Care and Topical Skin Care Compositions

The copolymers of the present invention can be formulated into a widevariety of product types, including mousses, gels, lotions, creams,ointments, tonics, sprays, aerosols, shampoos, conditioners, rinses, barsoaps, hand and body lotions, facial moisturizers, solid gel sticks,sunscreens, anti-acne preparations, topical analgesics, mascaras,antiperspirants, deodorants and the like. Carriers optionally used toformulate such product types should be immiscible with the volatilehydrophobic solvent component The term "immiscible" as used herein meansthe volatile, hydrophobic solvent component has a solubility in thecarrier of less than 2% by weight, preferably less than 1%, mostpreferably less than 0.1% such that at least two liquid phases areformed upon combining the volatile, hydrophobic solvent component withthe carrier. The optional Carriers and additional components vary withthe product type and can be routinely chosen by one skilled in the art.The following is a description of some of these carriers and additionalcomponents.

Hair Care Compositions

The hair care compositions of the present invention can comprise acarrier, or a mixture of such carriers, which are suitable forapplication to the hair. The carriers are preferably present at fromabout 0.5% to about 99.5%, preferably from about 5.0% to about 99.5%,more preferably from about 10.0% to about 98.0%, of the composition. Asused herein, the phrase "suitable for application to hair" means thatthe carrier does not damage or negatively affect the aesthetics of hairor cause irritation to the underlying skin.

Carriers suitable for use with hair care compositions of the presentinvention include, for example, those used in the formulation of hairsprays, mousses, tonics, gels, shampoos, conditioners, and rinses. Thechoice of appropriate carrier will also depend on the particularcopolymer to be used, and whether the product formulated is meant to beleft on the surface to which it is applied (e.g., hair spray, mousse,tonic, or gel) or rinsed off after use (e.g., shampoo, conditioner,rinse).

The carriers used herein can include a wide range of componentsconventionally used in hair care compositions. The carriers can containa solvent to dissolve or disperse additional copolymers being used, withwater, the C1-C6 alcohols, and mixtures thereof being preferred; andwater, methanol, ethanol, isopropanol, and mixtures thereof being morepreferred. The carriers can also contain a wide variety of additionalmaterials including, but not limited to acetone, hydrocarbons (such asisobutane, hexane, decene), halogenated hydrocarbons (such as Freons),lina-lool, esters (such as ethyl acetate, dibutyl phthalate), andvolatile silicon derivatives (especially siloxanes such as phenylpentamethyl disiloxane, methoxypropyl heptamethyl cyclotetrasiloxane,chloropropyl pentamethyl disiloxane, hydroxypropyl pentamethyldisiloxane, octamethyl cyclotetrasiloxane, decamethylcyclopentasiloxane, cyclomethicone, and dimethicone having for example,a viscosity at 25° C. of about 2.5 centipoise or less), and mixturesthereof. When the hair care composition is a hair spray, tonic, gel, ormousse the preferred solvents include water, ethanol, volatile siliconederivatives, and mixtures thereof. The solvents used in such mixes maybe miscible or immiscible with each other. Mousses and aerosol hairsprays can also utilize any of the conventional propellants to deliverthe material as a foam (in the case of a mousse) or as a fine, uniformspray (in the case of an aerosol hair spray). Examples of suitablepropellants include materials such as trichlorofluoromethane,dichlorodifluoromethane, difluoroethane, dimethylether, propane,n-butane or isobutane. A tonic or hair spray product having a lowviscosity may also utilize an emulsifying agent. Examples of suitableemulsifying agents include nonionic, cationic, anionic surfactants, ormixtures thereof. Fluorosurfactants are especially preferred,particularly if the product is a hair spray composition and mostespecially if it is a spray composition having relatively low levels ofvolatile organic solvents, such as alcohols, and relatively high levelsof water (e.g., in excess of about 10%, by weight water). If such anemulsifying agent is used, it is preferably present at a level of fromabout 0.01% to about 7.5% of the composition. The level of propellantcan be adjusted as desired but is generally from about 3% to about 30%of mousse compositions and from about 15% to about 70% of the aerosolhair spray compositions.

Suitable spray containers are well known in the art and includeconventional, non-aerosol pump sprays i.e., "atomizers," aerosolcontainers or cans having propellant, as described above, and also pumpaerosol containers utilizing compressed air as the propellant Pumpaerosol containers are disclosed, for example, in U.S. Pat. Nos.4,077,441, Mar. 7, 1978, Olofsson and 4,850,577, Jul. 25, 1989,TerStege, both incorporated by reference herein, and also in U.S. Ser.No. 07/839,648, Gosselin, Lund, Sojka, and Lefebvre, filed Feb. 21,1992, "Consumer Product Package Incorporating A Spray Device UtilizingLarge Diameter Bubbles. Pump aerosols hair sprays using compressed airare also currently marketed by The Procter & Gamble Company under theirtradename VIDAL SASSOON AIRSPRAY® hair sprays.

Where the hair care compositions are conditioners and rinses, thecarrier can include a wide variety of conditioning materials. Where thehair care compositions are shampoos, the carrier can includesurfactants, suspending agents, thickeners etc. Various additionalcomponents useful in hair care compositions are described in U.S. Pat.No. 5,106,609, to Bolich, Jr. et al., issued Apr. 21, 1992; and U.S.Pat. No. 4,387,090, to Bolich, Jr. issued Jun. 7, 1983; which areincorporated by reference herein. Some of these additional componentsare described below.

Topical Skin Care Compositions

The topical cosmetic and pharmaceutical compositions of the presentinvention can comprise a carrier. The carrier should be "cosmeticallyand/or pharmaceutically acceptable", which means that the carrier issuitable for topical application to the skin, has good aestheticproperties, is compatible with the copolymers of the present inventionand any other components, and will not cause any untoward safety ortoxicity concerns.

The carrier can be in a wide variety of forms. For example, emulsioncarriers, including, but not limited to, oil-in-water, water-in-oil,water-in-oil-in-water, and oil-in-water-in-silicone emulsions, areuseful herein. These emulsions can cover a broad range of viscosities,e.g., from about 100 cps to about 200,000 cps. These emulsions can alsobe delivered in the form of sprays using either mechanical pumpcontainers or pressurized aerosol containers using conventionalpropellants. These carriers can also be delivered in the form of amousse. Other suitable topical carriers include anhydrous liquidsolvents such as oils, alcohols, and silicones (e.g., mineral oil,ethanol, isopropanol, dimethicone, cyclomethicone, and the like);aqueous-based single phase liquid solvents (e.g., hydro-alcoholicsolvent systems); and thickened versions of these anhydrous andaqueous-based single phase solvents (e.g., where the viscosity of thesolvent has been increased to form a solid or semi-solid by the additionof appropriate gums, resins, waxes, polymers, salts, and the like).Examples of topical carrier systems useful in the present invention aredescribed in the following four references all of which are incorporatedherein by reference in their entirety: "Sun Products Formulary"Cosmetics & Toiletries, vol. 105, pp. 122-139 (December1990); "SunProducts Formulary", Cosmetics & Toiletries, vol. 102, pp. 117-136(March 1987); U.S. Pat. No. 4,960,764 to Figueroa et al., issued Oct. 2,1990; and U.S. Pat. No. 4,254,105 to Fukuda et al., issued Mar. 3, 1981.

The carriers of the skin care compositions preferably comprise fromabout 50% to about 99% by weight of the compositions of the presentinvention, more preferably from about 75% to about 99%, and mostpreferably from about 85% to about 95%.

Preferred cosmetically and/or pharmaceutically acceptable topicalcarriers include hydro-alcoholic systems and oil-in-water emulsions.When the carrier is a hydro-alcoholic system, the carrier can comprisefrom about 1% to about 50% of ethanol, isopropanol, or mixtures thereof,and from about 40% to about 99% of water. More preferred is a carriercomprising from about 5% to about 60% of ethanol, isopropanol, ormixtures thereof, and from about 40% to about 95% of water. Especiallypreferred is a carrier comprising from about 20% to about 50% ofethanol, isopropanol, or mixtures thereof, and from about 50% to about80% of water. When the carrier is an oil-in-water emulsion, the carriercan include any of the common excipient ingredients for preparing theseemulsions. Additional components useful in formulating these topicalcompositions are further described below.

Additional Components

A wide variety of additional components can be employed in the hair careand topical skin compositions herein. Non-limiting examples include thefollowing:

Pharmaceutical Actives

The compositions of the present invention, especially the topical skincare compositions, can comprise a safe and effective amount of apharmaceutical active. The phrase "safe and effective amount", as usedherein, means an amount of an active high enough to significantly orpositively modify the condition to be treated, but low enough to avoidserious side effects (at a reasonable benefit/risk ratio), within thescope of sound medical judgment. A safe and effective amount of thepharmaceutical active will vary with the specific active, the ability ofthe composition to penetrate the active through the skin, the amount ofcomposition to be applied, the particular condition being treated, theage and physical condition of the patient being treated, the severity ofthe condition, the duration of the treatment, the nature of concurrenttherapy, and like factors.

The pharmaceutical actives which can be used in the compositions of thepresent invention preferably comprise from about 0.1% to about 20% byweight of the compositions, more preferably from about 0.1% to about10%, and most preferably from about 0.1% to about 5%. Mixtures ofpharmaceutical actives may also be used.

Nonlimiting examples of pharmaceutical actives can include thefollowing:

Useful pharmaceutical actives in the compositions of the presentinvention include anti-acne actives. Anti-acne actives preferred for usein the present invention include the keratolytics such as salicylicacid, sulfur, lactic acid, glycolic, pyruvic acid, urea, resorcinol, andN-acetylcysteine; retinoids such as retinoic acid and its derivatives(e.g., cis and trans); antibiotics and antimicrobials such as benzoylperoxide, octopirox, erytlromycin, zinc, tetracyclin, triclosan, azelaicacid and its derivatives, phenoxy ethanol and phenoxy proponol,ethylacetate, clindamycin and meclocycline; sebostats such asflavinoids; alpha and beta hydroxy acids; and bile salts such as scymmolsulfate and its derivatives, deoxycholate, and cholate. Preferred foruse herein is salicylic acid.

Useful pharmaceutical actives in the compositions of the presentinvention include analgesic actives. Analgesic actives suitable for usein the present compositions include salicylic acid derivatives such asmethyl-salicylate, species and derivatives of the genus capsicum such ascapsaicin and non-steroidal anti-inflammatory drugs (NSAIDS). The NSAIDScan be selected from the following categories: propionic acidderivatives; acetic acid derivatives; fenamic acid derivatives;biphenylcarboxylic acid derivatives; and oxicams. All of these NSAIDSare fully described in the U.S. Pat. No. 4,985,459 to Sunshine et al.,issued Jan. 15, 1991, incorporated by reference herein. Most preferredare the propionic NSAIDS including but not limited to aspirin,acetaminophen, ibuprofen, naproxen, benoxaprofen, flurbiprofen,fenoprofen, fenbufen, ketoprofen, indoprofen, pirprofen, carprofen,oxaprozin, pranoprofen, miroprofen, tioxaprofen, suprofen, alminoprofen,tiaprofenic acid, fluprofen and bucloxic acid. Also useful are thesteroidal anti-inflammatory drugs including hydrocortisone and the like.

Useful pharmaceutical actives in the compositions of the presentinvention include antipruritic drugs. Antipruritic actives preferred forinclusion in compositions of the present invention includepharmaceutically-acceptable salts of methdilizine and trimeprazine.Useful pharmaceutical actives in the compositions of the presentinvention include anesthetic actives. Anesthetic actives preferred forinclusion in compositions of the present invention includepharmaceutically-acceptable salts of lidocaine, bupivacaine,chlorprocaine, dibucaine, etidocaine, mepivacaine, tetracaine,dyclonine, hexylcaine, procaine, cocaine, ketamine, pramoxine andphenol. Useful pharmaceutical actives in the compositions of the presentinvention include antimicrobial actives (antibacterial, antifungal,antiprotozoal and antiviral drugs). Antimicrobial actives preferred forinclusion in compositions of the present invention includepharmaceutically-acceptable salts of b-lactam drugs, quinolone drugs,ciprofloxacin, norfloxacin, tetracycline, erythromycin, amikacin,triclosan, doxycycline, capreomycin, chlorhexidine, chlortetracycline,oxytetracycline, clindamycin, ethambutol, metronidazole, pentamidine,gentamicin, kanamycin, lineomycin, methacycline, methenamine,minocycline, neomycin, netilmicin, paromomycin, streptomycin,tobramycin, miconazole and amanfadine. Antimicrobial drugs preferred forinclusion in compositions of the present invention include tetracyclinehydrochloride, erythromycin estolate, erythromycin stearate (salt),amikacin sulfate, doxycycline hydrochloride, capreomycin sulfate,chlorhexidine gluconate, chlorhexidine hydrochloride, chlortetracyclinehydrochloride, oxytetracycline hydrochloride, clindamycin hydrochloride,ethambutol hydrochloride, metronidazole hydrochloride, pentamidinehydrochloride, gentamicin sulfate, kanamycin sulfate, lineomycinhydrochloride, methacycline hydrochloride, methenamine hippurate,methenamine mandelate, minocycline hydrochloride, neomycin sulfate,netilmicin sulfate, paromomycin sulfate, streptomycin sulfate,tobramycin sulfate, miconazole hydrochloride, amanfadine hydrochloride,amanfadine sulfate, triclosan, octopirox, parachlorometa xylenol,nystatin, tolnaftate and clotrimazole.

Also useful herein are sunscreening agents. A wide variety ofsunscreening actives are described in U.S. Pat. No. 5,087,445, to Haffeyet al., issued Feb. 11, 1992; U.S. Pat. No. 5,073,372, to Turner et al.,issued Dec. 17, 1991; U.S. Pat. No. 5,073,371, to Turner et al. issuedDec. 17, 1991; and Segarin, et al., at Chapter VIII, pages 189 et seq.,of Cosmetics Science and Technology, all of which are incorporatedherein by reference in their entirety. Preferred among those sunscreenswhich are useful in the compositions of the instant invention are thoseselected from the group consisting of 2-ethylhexyl p-methoxycinnamate,2-ethylhexyl N,N-dimethyl-p-aminobenzoate, p-aminobenzoic acid,2-phenylbenzimidazole-5-sulfonic acid, octocrylene, oxybenzone,homomenthyl salicylate, octyl salicylate,4,4'-methoxy-t-butyldibenzoylmethane, 4-isopropyl dibenzoylmethane,3-benzylidene camphor, 3-(4-methylbenzylidene) camphor, titaniumdioxide, zinc oxide, silica, iron oxide, and mixtures thereof.

Still other useful sunscreens are those disclosed in U.S. Pat. No.4,937,370, to Sabatelli, issued Jun. 26, 1990; and U.S. Pat. No.4,999,186, to Sabatelli et al., issued Mar. 12, 1991; these tworeferences are incorporated by reference herein in their entirety. Thesunscreening actives disclosed therein have, in a single molecule, twodistinct chromophore moieties which exhibit different ultra-violetradiation absorption spectra. One of the chromophore moieties absorbspre-dominantly in the UVB radiation range and the other absorbs stronglyin the UVA radiation range. These sunscreening actives provide higherefficacy, broader UV absorption, lower skin penetration and longerlasting efficacy relative to conventional sunscreens. Especiallypreferred examples of these sunscreens include those selected from thegroup consisting of 4-N,N-2-ethylhexyl)methylaminobenzoic acid ester of2,4-dihydroxybenzophenone, 4-N,N-(2-ethylhexyl)methylaminobenzoic acidester with 4-hydroxydibenzoylmethane,4-N,N-(2-ethylhexyl)methylaminobenzoic acid ester of2-hydroxy-4-(2-hydroxyethoxy)benzophenone,4-N,N-(2-ethylhexyl)-methylaminobenzoic acid ester of4-(2-hydroxyethoxy)dibenzoylmethane, and mixtures thereof.

Generally, the sunscreens can comprise from about 0.5% to about 20% ofthe compositions useful herein. Exact amounts will vary depending uponthe sunscreen chosen and the desired Sun Protection Factor (SPF). SPF isa commonly used measure of photoprotection of a sunscreen againsterythema. See Federal Register, Vol. 43, No. 166, pp. 38206-38269, Aug.25, 1978, which is incorporated herein by reference in its entirety.

Also useful in the present invention are sunless tanning activesincluding dihydroxyacetone, glyceraldehyde, indoles and theirderivatives, and the like. These sunless tanning actives may also beused in combination with the sunscreen agents.

Other useful actives include skin bleaching (or lightening) activesincluding but not limited to hydroquinone, ascorbic acid, kojic acid andsodium metabisulfite.

Other useful actives which are especially useful for hair carecompositions include anti-dandruff actives such as zinc pyrithione,octopirox, selenium disulfide, sulfur, coal tar, and the like.

Other useful actives include antiperspirant actives. Suitable for useherein are those which comprise any compound, composition or mixturethereof having antiperspirant activity. Astringent metallic salts arepreferred antiperspirant materials for use herein, particularly theinorganic and organic salts of aluminum, zirconium and zinc, as well asmixtures thereof. Particularly preferred are the aluminum and zirconiumsalts, such as aluminum halides, aluminum hydroxy halides, zirconyloxide halides, zirconyl hydroxy halides, and mixtures thereof.

Additionally, deodorant actives in the form of bacteriostats may beincorporated into the present compositions. Suitable deodorantbacteriostats include 2,2'-methylenebis(3,4,6-trichlorophenol),2,4,4'-trichloro-2'-hydroxy(diphenyl ether), zinc phenolsulfonate,2,2'-thiobis(4,6-dichlorophenol), p-chloro-m-xylenol, dichloro-m-xylenoland the like. Most preferred is 2,4,4'-trichloro-2'-hydroxy(diphenylether), which is generically known as triclosan and available from theCiba-Geigy Corporation under the trademark, Irgasan DP-300 RegisteredTM. When triclosan is utilized it will be present in a range from about0.05 to about 0.9%, preferably from about 0.1 to about 0.5% by weight ofthe composition. Other types of bacteriostats include sodium N-lauroylsarcosine, sodium N-palmitoyl sarcosine, lauroyl sarcosine, N-myristoylglycine, potassium N-lauroyl sarcosine and aluminum chlorhydroxy lactate(sold by Reheis Chemical Company under trademark of Chloracel).

Conditioners

Conditioning agents useful herein, and especially useful for hair carecompositions, include hydrocarbons, silicone fluids, and cationicmaterials.

The hydrocarbons can be either straight or branched chain and cancontain from about 10 to about 16, preferably from about 12 to about 16carbon atoms. Examples of suitable hydrocarbons are decane, dodecane,tetradecane, tridecane, and mixtures thereof.

Silicone conditioning agents useful herein can include either cyclic orlinear polydimethylsiloxanes, phenyl and alkyl phenyl silicones, andsilicone copolyols. The linear volatile silicones generally haveviscosities of less than about 5 centistokes at 25° C., while the cyclicmaterials have viscosities less than about 10 centistokes.

Cationic conditioning agents useful herein include quaternary ammoniumsalts or the salts of fatty amines. These additional cationic agents areused herein for the purpose of providing conditioning and are separateand apart from the complexing agents of the present invention. Preferredquaternary ammonium salts are dialkyl dimethyl ammonium chlorides,wherein the alkyl groups have from 12 to 22 carbon atoms and are derivedfrom long-chain fatty acids. Representative examples of quaternaryammonium salts include ditallow dimethyl ammonium chloride, ditallowdimethyl ammonium methyl sulfate, dihexadecyl dimethyl ammoniumchloride, and di(hydrogenated tallow) ammonium chloride. Otherquaternary ammonium salts useful herein are dicationics such as tallowpropane diammonium dichloride. Quaternary imidazolinium salts are alsouseful herein. Examples of such materials are those imidazolinium saltscontaining C12-22 alkyl groups such as 1-methyl-1-(stearoylamide)ethyl!-2-heptadecyl-4, 5-dihydroimidazolinium chloride,1-methyl-1- (palmitoylamide)ethyl!-2-octadecyl4,5-dihydroimidazoliniumchloride and 1-methyl-1- (tallowamide)-ethyl!-2-tallow-imidazoliniummethyl sulfate. Also useful herein are salts of fatty amines. Examplesof such compounds include stearylamine hydrochloride, soyaminehydrochloride, and stearylamine formate. Useful conditioning agents aredisclosed in U.S. Pat. No. 4,387,090, to Bolich, issued Jun. 7, 1983,which is incorporated by reference herein.

Humectants and Moisturizers

The compositions of the present invention can contain one or morehumectant or moisturizing materials. A variety of these materials can beemployed and each can be present at a level of from about 0.1% to about20%, more preferably from about 1% to about 10% and most preferably fromabout 2% to about 5%. These materials include urea; guanidine; glycolicacid and glycolate salts (e.g. ammonium and quaternary alkyl ammonium);lactic acid and lactate salts (e.g. ammonium and quaternary alkylammonium); aloe vera in any of its variety of forms (e.g., aloe veragel); polyhydroxy alcohols such as sorbitol glycerol, hexanetriol,propylene glycol, butylene glycol, hexylene glycol and the like;polyethylene glycols; sugars and starches; sugar and starch derivatives(e.g., alkoxylated glucose); hyaluronic acid; lactamidemonoethanolamine; acetamide monoethanolamine; and mixtures thereof.Preferred humectants and moisturizers are glycerol, butylene glycol,hexylene glycol, and mixtures thereof.

Surfactants

The compositions of the present invention, especially the shampoo andconditioner compositions, can contain one or more surfactants. Thesesurfactants are useful adjuncts for the carriers of the presentcompositions, and are not required for solubilizing, dispersing orcomplexing the copolymers of the present invention. For a shampoo, thelevel is preferably from about 10% to about 30%, preferably from 12% toabout 25%, of the composition. For conditioners, the preferred level ofsurfactant is from about 0.2% to about 3%. Surfactants useful incompositions of the present invention include anionic, nonionic,cationic, zwitterionic and amphoteric surfactants. A wide variety ofsurfactants useful herein are disclosed in U.S. Pat. No. 5,151,209, toMc Call et al., issued Sep. 29, 1992; U.S. Pat. No. 5,151,210, to Steuriet al., issued Sep. 29, 1992; and U.S. Pat. No. 5,120,532, to Wells etal., issued Jun. 9, 1992, all of which are incorporated by referenceherein.

Nonlimiting examples of these surfactants include anionic surfactantssuch as alkyl and alkyl ether sulfates. These materials typically havethe respective formulae ROSO₃ M and RO(C₂ H₄ O)_(x) SO₃ M, wherein R isalkyl or alkenyl of from about 10 to about 20 carbon atoms, x is 1 to10, and M is a water-soluble cation such as ammonium, sodium, potassiumand triethanolamine. Another suitable class of anionic surfactants arethe water-soluble salts of the organic, sulfuric acid reaction productsof the formula:

    R.sub.1--SO.sub.3 --M

wherein R₁ is chosen from the group consisting of a straight or branchedchain, saturated aliphatic hydrocarbon radical having from about 8 toabout 24, preferably about 12 to about 18, carbon atoms; and M is acation. Additional examples of anionic synthetic surfactants which comewithin the terms of the present invention are the reaction products offatty acids esterified with isethionic acid and neutralized with sodiumhydroxide where, for example, the fatty acids are derived from coconutoil; sodium or potassium salts of fatty acid amides of methyl tauride inwhich the fatty acids, for example, are derived from coconut oil. Stillother anionic synthetic surfactants include the class designated assuccinamates, olefin sulfonates having about 12 to about 24 carbonatoms, and b-alkyloxy alkane sulfonates. Many additional nonsoapsynthetic anionic surfactants are described in McCutcheon's, Detergentsand Emulsifiers, 1984 Annual published by Allured PublishingCorporation, which is incorporated herein by reference. Also U.S. Pat.No. 3,929,678, Laughlin et al., issued Dec. 30, 1975, discloses manyother anionic as well as other surfactant types and is incorporatedherein by reference.

Nonionic surfactants useful herein are preferably used in combinationwith an anionic, amphoteric or zwitterionic surfactant. These nonionicsurfactants can be broadly defined as compounds produced by thecondensation of alkylene oxide groups (hydrophilic in nature) with anorganic hydrophobic compound, which may be aliphatic or alkyl aromaticin nature.

Cationic surfactants useful in compositions of the present invention aredisclosed in the following documents, all incorporated by referenceherein: M.C. Publishing Co., McCutcheon's, Detergents & Emulsifiers,(North American edition 1979); Schwartz, et al., Surface Active Agents,Their Chemistry and Technology, New York: Interscience Publishers, 1949;U.S. Pat. No. 3,155,591, Hilfer, issued Nov. 3, 1964; U.S. Pat. No.3,929,678, Laughlin, et al., issued Dec. 30, 1975; U.S. Pat. No.3,959,461, Bailey, et al., issued May 25, 1976; and U.S. Pat. No.4,387,090, Bolich, Jr., issued Jun. 7, 1983. If included in thecompositions of the present invention, the cationic surfactant ispresent at from about 0.05% to about 5%.

Zwitterionic surfactants are exemplified by those which can be broadlydescribed as derivatives of aliphatic quaternary ammonium, phosphonium,and sulfonium compounds, in which the aliphatic radicals can be straightor branched chain, and wherein one of the aliphatic substituentscontains from about 8 to about 18 carbon atoms and one contains ananionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate,phosphate, or phosphonate. Other zwitterionics such as betaines are alsouseful in the present invention. Examples of betaines include the highalkyl betaines, such as coco dimethyl carboxymethyl betaine, lauryldimethyl carboxymethyl betaine, lauryl dimethyl alphacarboxyethylbetaine, cetyl dimethyl carboxymethyl betaine, laurylbis-(2-hydroxyethyl) carboxymethyl betaine, stearylbis-(2-hydroxypropyl) carboxymethyl betaine, oleyl di-methylgamma-carboxypropyl betaine, laurylbis-(2-hydroxypropyl)alpha-carboxyethyl betaine, coco dimethylsulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryldimethyl sulfoethyl betaine, lauryl bis-(2-hydroxyethyl) sulfopropylbetaine, and amidobetaines and amidosulfobetaines (wherein theRCONH(CH₂)₃ radical is attached to the nitrogen atom of the betaine).

Examples of amphoteric surfactants which can be used in the compositionsof the present invention are those which are broadly described asderivatives of aliphatic secondary and tertiary amines in which thealiphatic radical can be straight or branched chain and wherein one ofthe aliphatic substituents contains from about 8 to about 18 carbonatoms and one contains an anionic water solubilizing group, e.g.,carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples ofcompounds falling within this definition are sodium3-dodecyl-aminopropionate, sodium 3-dodecylaminopropane sulfonate,N-alkyltaurines such as the one prepared by reacting dodecylamine withsodium isethionate according to the teaching of U.S. Pat. No. 2,658,072,N-higher alkyl aspartic acids such as those produced according to theteaching of U.S. Pat. No. 2,438,091, and the products sold under thetrade name "Miranol" and described in U.S. Pat. No. 2,528,378.

Carboxylic Acid Copolymer Thickeners

Another component useful in the compositions herein is a carboxyliccopolymer thickener. These crosslinked polymers contain one or moremonomers derived from acrylic acid, substituted acrylic acids, and saltsand esters of these acrylic acids and the substituted acrylic acids,wherein the crosslinking agent contains two or more carbon-carbon doublebonds and is derived from a polyhydric alcohol. The preferred polymersfor use herein are of two general types. The first type of polymer is acrosslinked homopolymer of an acrylic acid monomer or derivative thereof(e.g., wherein the acrylic acid has substituents on the two and threecarbon positions independently selected from the group consisting ofC₁₋₄ allyl, --CN, --COOH and mixtures thereof). The second type ofpolymer is a crosslinked copolymer having a first monomer selected fromthe group consisting of an acrylic acid monomer or derivative thereof(as just described in the previous sentence), a short chain alcohol(i.e. a C₁₋₄) acrylate ester monomer or derivative thereof (e.g.,wherein the acrylic acid portion of the ester has substituents on thetwo and three carbon positions independently selected from the groupconsisting of C₁₋₄ alkyl, --CN, --COOH--, and mixtures thereof), andmixtures thereof; and a second monomer which is a long chain alcohol(i.e. C₈₋₄₀) acrylate ester monomer or derivative thereof (e.g., whereinthe acrylic acid portion of the ester has substituents on the two andthree carbon positions independently selected from the group consistingof C₁₋₄ alkyl, --CN, --COOH, and mixtures thereof). Combinations ofthese two types of polymers are also useful herein.

In the first type of crosslinked homopolymers the monomers arepreferably selected from the group consisting of acrylic acid,methacrylic acid, ethacrylic acid, and mixtures thereof, with acrylicacid being most preferred. In the second type of crosslinked copolymersthe acrylic acid monomer or derivative thereof is preferably selectedfrom the group consisting of acrylic acid, methacrylic acid, ethacrylicacid, and mixtures thereof, with acrylic acid, methacrylic acid, andmixtures thereof being most preferred. The short chain alcohol acrylateester monomer or derivative thereof is preferably selected from thegroup consisting of C₁₋₄ alcohol acrylate esters, C₁₋₄ alcoholmethacrylate esters, C₁₋₄ alcohol ethacrylate esters, and mixturesthereof, with the C₁₋₄ alcohol acrylate esters, C₁₋₄ alcoholmethacrylate esters, and mixtures thereof, being most preferred. Thelong chain alcohol acrylate ester monomer is selected from C₈₋₄₀ alkylacrylate esters, with C₁₀₋₃₀ alkyl acrylate esters being preferred.

The crosslinking agent in both of these types of polymers is apolyalkenyl polyether of a polyhydric alcohol containing more than onealkenyl ether group per molecule, wherein the parent polyhydric alcoholcontains at least 3 carbon atoms and at least 3 hydroxyl groups.Preferred crosslinkers are those selected from the group consisting ofallyl ethers of sucrose and allyl ethers of pentaeythritol, and mixturesthereof. These polymers useful in the present invention are more fullydescribed in U.S. Pat. No. 5,087,445, to Haffey et al., issued Feb. 11,1992; U.S. Pat. No. 4,509,949, to Huang et al., issued Apr. 5, 1985;U.S. Pat. No. 2,798,053, to Brown, issued Jul. 2, 1957; which areincorporated by reference herein. See also, CTFA International CosmeticIngredient Dictionary, fourth edition, 1991, pp. 12 and 80; which arealso incorporated herein by reference.

Examples of commercially available homopolymers of the first type usefulherein include the carbomers, which are homopolymers of acrylic acidcrosslinked with allyl ethers of sucrose or pentaerytritol. Thecarbomers are available as the Carbopol® 900 series from B. F. Goodrich.Examples of commercially available copolymers of the second type usefulherein include copolymers of C₁₀₋₃₀ alkyl acrylates with one or moremonomers of acrylic acid, methacrylic acid, or one of their short chain(i.e. C₁₋₄ alcohol) esters, wherein the crosslinking agent is an allylether of sucrose or pentaerytritol. These copolymers are known asacrylates/C10-30 alkyl acrylate crosspolymers and are commerciallyavailable as Carbopol® 1342, Pemulen TR-1, and Pemulen TR-2, from B. F.Goodrich. In other words, examples of carboxylic acid polymer thickenersuseful herein are those selected from the group consisting of carbomers,acrylates/C10-C30 alkyl acrylate crosspolymers, and mixtures thereof.

The compositions of the present can comprise from about 0.025% to about1%, more preferably from about 0.05% to about 0.75% and most preferablyfrom about 0.10% to about 0.50% of the carboxylic acid polymerthickeners.

Emulsifiers

The compositions herein can contain various emulsifiers. Theseemulsifiers are useful for emulsifying the various carrier components ofthe compositions herein, and are not required for solubilizing ordispersing the copolymers of the present invention. Suitable emulsifierscan include any of a wide variety of nonionic, cationic, anionic, andzwitterionic emulsifiers disclosed in the prior patents and otherreferences. See McCutcheon's, Detergents and Emulsifiers, North AmericanEdition (1986), published by Allured Publishing Corporation; U.S. Pat.No. 5,011,681 to Ciotti et al., issued Apr. 30, 1991; U.S. Pat. No.4,421,769 to Dixon et al., issued Dec. 20, 1983; and U.S. Pat. No.3,755,560 to Dickert et al., issued Aug. 28, 1973; these four referencesare incorporated herein by reference in their entirety.

Suitable emulsifier types include esters of glycerin, esters ofpropylene glycol, fatty acid esters of polyethylene glycol, fatty acidesters of polypropylene glycol, esters of sorbitol, esters of sorbitananhydrides, carboxylic acid copolymers, esters and ethers of glucose,ethoxylated ethers, ethoxylated alcohols, alkyl phosphates,polyoxyethylene fatty ether phosphates, fatty acid amides, acyllactylates, soaps and mixtures thereof.

Suitable emulsifiers can include, but are not limited to, polyethyleneglycol 20 sorbitan monolaurate (Polysorbate 20), polyethylene glycol 5soya sterol, Steareth-20, Ceteareth-20, PPG-2 methyl glucose etherdistearate, Ceteth-10, Polysorbate 80, cetyl phosphate, potassium cetylphosphate, diethanolamine cetyl phosphate, Polysorbate 60, glycerylstearate, PEG-100 stearate, and mixtures thereof. The emulsifiers can beused individually or as a mixture of two or more and can comprise fromabout 0.1% to about 10%, more preferably from about 1% to about 7%, andmost preferably from about 1% to about 5% of the compositions of thepresent invention.

Emollients

The compositions useful in the methods of the present invention can alsooptionally comprise at least one emollient. Examples of suitableemollients include, but are not limited to, volatile and non-volatilesilicone oils, highly branched hydrocarbons, and non-polar carboxylicacid and alcohol esters, and mixtures thereof. Emollients useful in theinstant invention are further described in U.S. Pat. No. 4,919,934, toDeckner et al., issued Apr. 24 1990, which is incorporated herein byreference in its entirety.

The emollients can typically comprise in total from about 1% to about50%, preferably from about 1% to about 25%, and more preferably fromabout 1% to about 10% by weight of the compositions useful in thepresent invention.

Additional Components

A variety of additional components can be incorporated into thecompositions herein. Nonlimiting examples of these additional componentsinclude vitamins and derivatives thereof (e.g., ascorbic acid, vitaminE, tocopheryl acetate, retinoic acid, retinol, retinoids, and the like);low pH thickening agents (e.g. polyacrylamide and C₁₃₋₁₄ isoparaffin andlaureth-7, available as Sepigel from Seppic Corporation; polyquaterniumand mineral oil, available as Salcare SC92, from Allied Colloids;crosslinked methyl quaternized dimethylaminomethacrylate and mineraloil, available as Salcare SC95 from Allied Colloids; resins; gums andthickeners such as xanthan gum, carboxymethyl cellulose, hydroxymethylcellulose, hydroxyethyl cellulose, alkyl-modified hydroxyalkylcelluloses (e.g. long chain allyl modified hydroxyethyl celluloses suchas cetyl hydroxyethylcellulose), and magnesium aluminum silicate;cationic polymers and thickeners (e.g., cationic guar gum derivativessuch as guar hydroxypropyltrimonium chloride and hydroxypropyl guarhydroxypropyltrimonium chloride, available as the Jaguar C series fromRhone-Poulenc; polymers for aiding the film-forming properties andsubstantivity of the composition (such as a copolymer of eicosene andvinyl pyrrolidone, an example of which is available from GAF ChemicalCorporation as Ganex® V-220); suspending agents such as ethylene glycoldistearate and the like; preservatives for maintaining the antimicrobialintegrity of the compositions; skin penetration aids such as DMSO,1-dodecylazacycloheptan-2-one (available as Azone from the Upjohn Co.)and the like; antioxidants; chelators and sequestrants; and aestheticcomponents such as fragrances, colorings, essential oils, skin sensates,astringents, skin soothing agents, skin healing agents and the like,nonlimiting examples of these aesthetic components include panthenol andderivatives (e.g. ethyl panthenol), pantothenic acid and itsderivatives, clove oil, menthol, camphor, eucalyptus oil, eugenol,menthyl lactate, witch hazel distillate, allantoin, bisabalol,dipotassium glycyrrhizinate and the like.

Method of Using Hair and Skin Care Compositions

The hair care and skin care compositions of the present invention areused in conventional ways to provide the desired benefit appropriate tothe product such as hair styling, holding, cleansing, conditioning andthe like for hair care compositions and benefits such as moisturization,sun protection, anti-acne, anti-wrinkling, artificial tanning,analgesic, and other cosmetic and pharmaceutical benefits for skin carecompositions. Such methods of use depend upon the type of compositionemployed but generally involve application of an effective amount of theproduct to the hair or skin, which may then be rinsed from the hair orskin (as in the case of shampoos and some conditioning products) orallowed to remain on the hair (as in the case of spray, mousse, or gelproducts), or allowed to remain on the skin (as in the case of the skincare compositions). By "effective amount" is meant an amount sufficientto provide the benefit desired. Preferably, hair rinse, mousse, and gelproducts are applied to wet or damp hair prior to drying and styling ofthe hair. After such compositions are applied to the hair, the hair isdried and styled in the usual ways of the user. Hair sprays aretypically applied to dry hair after it has already been dried andstyled. Cosmetic and pharmaceutical topical skin care compositions areapplied to and rubbed into the skin.

EXAMPLES

The following examples further illustrate preferred embodiments withinthe scope of the present invention. The examples are given solely forthe purposes of illustration and are not to be construed as limitationsof the present invention as many variations of the invention arepossible without departing from its spirit and scope.

Ingredients are identified by chemical or CTFA name.

The following synthetic procedure is exemplary of the methods useful forsynthesizing the copolymers of the present invention.

Example 1

Synthesis of Poly (t-butyl acrylate)-(acrylicacid-graft-polydimethylsiloxane)!

Place 60 parts of t-butyl acrylate, 20 parts acrylic acid and 20 partsof polydimethylsiloxane macromonomer (13,000 MW) (commercially availablefrom 3M St. Paul, Minn.) in a flask. Add sufficient acetone as thereaction solvent to produce a final monomer concentration of 20%. Purgethe vessel with an inert atmosphere, preferably nitrogen or argon. Addinitiator, (2,2'-azobisisobutyronitrile) to a level appropriate for thedesired molecular weight. Typically this is in the range of about 0.5%to about 1.0% by weight relative to the amount of monomer. Heat to 60°C. and maintain this temperature for 6 hours while agitating. Terminatethe reaction by cooling to room temperature. The polymer is purified bydrying off the reaction solvent in an oven.

Example 2

Synthesis of Poly (t-butyl acrylate)-(methacrylicacid)-graft-polydimethylsiloxane)!

Place 70 parts of t-butyl acrylate, 10 parts methacrylic acid and 20parts of polydimethylsiloxane macromonomer (13,000 MW) (commerciallyavailable from 3M, St. Paul, Minn.) in a flask. Add sufficient acetoneas the reaction solvent to produce a final monomer concentration of 20%.Purge the vessel with an inert atmosphere, preferably nitrogen or argon.Add initiator, (2,2'-azobisisobutyronitrile) to a level appropriate forthe desired molecular weight. Typically this is in the range of about0.5% to about 1.0% by weight relative to the amount of monomer. Heat to60° C. and maintain this temperature for 6 hours while agitating.Terminate the reaction by cooling to room temperature. The polymer ispurified by drying off the reaction solvent in an oven.

Example 3

Synthesis of Poly (t-butyl acrylate)-(methacrylic acid)-(2-ethylhexylmethacrylate)!

Place 70 parts of t-butyl acrylate, 10 parts methacrylic acid and 20parts of 2-ethylhexylmethacrylate in a flask. Add sufficient acetone asthe reaction solvent to produce a final monomer concentration of 20%.Purge the vessel with an inert atmosphere, preferably nitrogen or argon.Add initiator, (2,2'-azobisisobutyronitrile) to a level appropriate forthe desired molecular weight. Typically this is in the range of about0.5% to about 1.0% by weight relative to the amount of monomer. Heat to60° C. and maintain this temperature for 6 hours while agitating.Terminate the reaction by cooling to room temperature. The polymer ispurified by drying off the reaction solvent in an oven.

Example 4

Synthesis of Poly (t-butyl acrylate)acrylicacid)-graft-polyisobutylene)!

Place 60 parts of t-butyl acrylate, 20 parts acrylic acid and 20 partsof polyisobutylene macromonomer in a flask. Add sufficient acetone asthe reaction solvent to produce a final monomer concentration of 20%.Purge the vessel with an inert atmosphere, preferably nitrogen or argon.Add initiator, (2,2'-azobisisobutyronitrile) to a level appropriate forthe desired molecular weight. Typically this is in the range of about0.5% to about 1.0% by weight relative to the amount of monomer. Heat to60° C. and maintain this temperature for 6 hours while agitating.Terminate the reaction by cooling to room temperature. The polymer ispurified by drying off the reaction solvent in an oven.

Example 5

Synthesis of Poly (t-butyl acrylate)-(methacrylicacid)-graft-polyisobutylene)!

Place 70 parts of t-butyl acrylate, 10 parts methacrylic acid and 20parts of polyisobutylene macromonomer in a flask. Add sufficient acetoneas the reaction solvent to produce a final monomer concentration of 20%.Purge the vessel with an inert atmosphere, preferably nitrogen or argon.Add initiator, (2,2'-azobisisobutyronitrile) to a level appropriate forthe desired molecular weight. Typically this is in the range of about0.5% to about 1.0% by weight relative to the amount of monomer. Heat to60° C. and maintain this temperature for 6 hours while agitating.Terminate the reaction by cooling to room temperature. The polymer ispurified by drying off the reaction solvent in an oven.

Example 6

Synthesis of Poly (t-butyl acrylate)-(methacrylic acid)-(2-ethylhexylmethacrylate)!

Place 70 parts of t-butyl acrylate, 10 parts methacrylic acid and 20parts of 2-ethylhexylmethacrylate in a flask. Add sufficient acetone asthe reaction solvent to produce a final monomer concentration of 20%.Purge the vessel with an inert atmosphere, preferably nitrogen or argon.Add initiator, (2,2'-azobisisobutyronitrile) to a level appropriate forthe desired molecular weight. Typically this is in the range of about0.5% to about 1.0% by weight relative to the amount of monomer. Heat to60° C. and maintain this temperature for 6 hours while agitating.Terminate the reaction by cooling to room temperature. The polymer ispurified by drying off the reaction solvent in an oven.

By varying the monomers and macromonomers used, the general proceduresgiven above in Examples 1-6, is used to prepare other copolymers of thepresent invention.

Example 7

The following is a hair conditioner composition representative of thepresent invention.

    ______________________________________    Component               Weight %    ______________________________________    Water                   Q.S. to 100%    Hydrophobically Modified Hydroxyethylcellulose.sup. 1!                            0.25%    Stearalkonium Chloride  0.87%    Cetyl Alcohol           1.85%    Stearyl Alcohol         0.21%    Stearamidopropyl Dimethylamine                            0.50%    CF1213 ®.sup. 2!    2.33%    Methylchloroisothiazolinone Methylisothiazolinone                            0.03%    Perfume                 0.33%    Copolymer 3.sup. 3!     2.00%    Dimethylmyristamine (ARMEEN DM14D).sup. 4!                            0.56%    Cyclomethicone D4       9.63%    ______________________________________     .sup. 1! Polysurf 67 ® supplied by Aqualon     .sup. 2! Dimethicone Gum in D5 cyclomethicone; commercially available fro     GE     .sup. 3! Poly tbutyl acrylate)(methacrylic acid)(2-ethylhexylmethacrylate     .sup. 4! Commercially available from Akzo

This product is prepared by dispersing the copolymer in CyclomethiconeD4 (solvent component) then adding the dimethylmyristamine. Heat thesolution to 65° C. and use an appropriate homogenizer to facilitateincorporation of the copolymer into the solvent component. The othercomponents (except Kathon and perfume) are mixed in a separate vessel ata temperature high enough (80° C.) to melt the solids. Thepolymer/solvent component mixture and the CF1213® are added separatelyto the other components after those have been cooled to at least 45° C.Finally, Kathon and perfume are added, and the product cooled toambient. This composition is useful for application to the hair toprovide conditioning, styling and hold benefits.

Example 8

The following is a hair conditioner composition representative of thepresent invention.

    ______________________________________    Component                 Weight %    ______________________________________    Water                     Q.S. to 100%    Hydrophobically Modified Hydroxyethylcellulose.sup. 1!                              0.50%    Stearalkonium Chloride    0.87%    Cetyl Alcohol             1.85%    Stearyl Alcohol           0.21%    Stearamidopropyl Dimethylamine                              0.50%    CF1213 ®.sup. 2!      2.33%    Methylchloroisothiazolinone Methylisothiazolinone                              0.03%    Perfume                   0.33%    Copolymer 1.sup. 3!       2.00%    dimethyllauramine (ARMEENDM12D).sup. 4!                              1.18%    Isododecane               4.81%    Hexamethyl disiloxane     4.81%    ______________________________________     .sup. 1! Polysurf 67 ® supplied by Aqualon     .sup. 2! Dimethicone Gum in D5 cyclomethicone; commercially available fro     GE     .sup. 3! Poly (tbutyl acrylate)(acrylic acid)graft polydimethylsiloxane)     .sup. 4! Available from Akzo

This product is prepared by dispersing the copolymer in Isododecane andhexamethyl disiloxane (solvent component) then adding thedimethyllauramine. Heat the solution to 65° C. and use an appropriatehomogenizer to facilitate incorporation of the copolymer into thesolvent component. The other components (except Kathon and perfume) aremixed in a separate vessel at a temperature high enough (80° C.) to meltthe solids. The polymer/solvent component mixture and the dimethiconegum are added separately to the other components after those have beencooled to at least 45° C. Finally, Kathon and perfume are added, and theproduct cooled to ambient. This composition is useful for application tothe hair to provide conditioning, styling and hold benefits.

Example 9

The following is a hair shampoo composition representative of thepresent invention.

    ______________________________________    Component               Weight %    ______________________________________    Water                   Q.S. to 100%    Ammonium Lauryl Sulfate 3.14%    Ammonium Laureth Sulfate                            13.56%    Cetyl Alcohol           0.45%    Stearyl Alcohol         0.19%    Coco Monoethanol Amide  3.00%    Ethylene Glycol Distearate                            2.00%    Tricetyl Methyl Ammonium Chloride                            0.50%    Methylchloroisothiazolinone Methylisothiazolinone                            0.03%    Perfume                 0.20%    Copolymer 2.sup. 1!     4.00%    Stearamine (ARMEEN 18).sup. 2!                            1.25%    Isododecane             7.40%    ______________________________________     .sup. 1! Poly (tbutyl acrylate)(methacrylic     acid)graft-polydimethylsiloxane)     .sup. 2! Commercially available from Akzo

This product is prepared by dispersing the copolymer in isododecane(solvent component) then adding the stearamine. Heat the solution to 65°C. and use an appropriate homogenizer to facilitate incorporation of thecopolymer into the solvent component. The other components are mixed ina separate vessel at a temperature high enough to melt the solids. Thepolymer/solvent component mixture is added to the other components afterthose have been cooled. This composition is useful for application tothe hair to provide cleansing, styling and hold benefits.

Example 10

The following is a hair shampoo composition representative of thepresent invention.

    ______________________________________    Component               Weight %    ______________________________________    Water                   Q.S. to 100%    Cocoamidopropyl Betaine 8.30%    Ammonium Lauryl Sulfate 2.12%    Ammonium Laureth Sulfate                            6.35%    Coco Monoethanol Amide  1.50%    Hydroxypropyl Methocellulose (K15)                            0.25%    Ethylene Glycol Distearate                            1.50%    Tricetyl Methyl Ammonium Chloride                            0.50%    Methylchloroisothiazolinone Methylisothiazolinone                            0.03%    Perfume                 0.20%    Copolymer 4.sup. 1!     3.00%    dimethylstearamine (ARMEEN DM18D).sup. 2!                            2.48%    Isododecane             5.00%    Cyclomethicone          5.00%    ______________________________________     .sup. 1! Poly (tbutyl acrylate)(acrylic acid)grift-polyisobutylene)     .sup. 2! Commercially available from Akzo

This product is prepared by dispersing the copolymer in isododecane andcyclomethicone (solvent component) then adding the dimethylstearamine.Heat the solution to 65° C. and use an appropriate homogenizer tofacilitate incorporation of the copolymer into the solvent component.The other components are mixed in a separate vessel at a temperaturehigh enough to melt the solids. The polymer/solvent component solutionis added to the other components after those have been cooled.

Example 11

The following is a hair styling gel composition representative of thepresent invention.

    ______________________________________    Component              Weight %    ______________________________________    Polymer-Solvent component Mix    Copolymer 5.sup. 1!    1.25%    dimethylpalmitamine    0.39%    Isopar H ®.sup. 2! 3.75%    Premix    Water                  43.00%    Hydrogenated Ditallowdimonium Chloride                           1.00%    (Quaternium 18)    Main Mix    Water                  48.47%    Carbopol 940 ®     0.75%    Triethanol Amine       1.00%    Panthenol              0.05%    Perfume                0.20%    ______________________________________     .sup. 1! Poly (tbutyl acrylate)(methacrylic acid)graft-polyisobutylene)     .sup. 2! C.sub.11 -C.sub.12 Isoparaffin, available from Exxon Chemical Co

This product is prepared by dispersing the copolymer in Isopar H®(solvent component) then adding the dimethylpalmitamie. Heat thesolution to 65° C. and use an appropriate homogenizer to facilitateincorporation of the copolymer into the solvent component. Quaternium 18is mixed with water at 80° C. The polymer-solvent component mixture isadded to the Quaternium 18 containing premix at either high or lowtemperature. The other components are mixed in a separate vessel atambient temperature. The Quaternium 18 premix with the polymer/solventcomponent mixture is cooled (if needed) and added to the othercomponents. This composition is useful for application to the hair toprovide conditioning, styling and hold benefits.

Example 12

The following is a spray-on gel hair composition representative of thepresent invention.

    ______________________________________    Component             Weight %    ______________________________________    Water                 Q.S. to 100%    Tallowtrimonium Chloride                          0.10%    Hydrogenated Ditallowdimonium Chloride                          0.90%    (Quaternium 18)    Panthenol             0.05%    Perfume               0.20%    Copolymer 6.sup. 1!   1.00%    myristamine           0.25%    Hexamethyl disiloxane 3.00%    ______________________________________     .sup. 1! Poly (tbutyl acrylate)(methacrylic     acid)(2-ethylhexylmethacrylate)

This product is prepared by dissolving the copolymer in hexamethyldisiloxane (solvent component) then adding the myristamine. Heat thesolution to 65° C. and use an appropriate homogenizer to facilitateincorporation of the copolymer into the solvent component. The othercomponents are mixed in a separate vessel at a temperature high enough(70° C.) to melt the solids. The polymer/solvent component solution isadded to the other components at either high or low temperature. Thiscomposition is useful for application to the hair to provideconditioning, styling and hold benefits.

Example 13

The following is a hair styling rinse composition representative of thepresent invention.

    ______________________________________    Component                 Weight %    ______________________________________    Premix A    Water                     8.14%    Ditallowdimonium Chloride (Varisoft 470)                              1.43%    CF1213 ®.sup. 1!      2.33%    Amodimethicone            0.10%    Premix B    Water                     5.45%    Stearalkonium Chloride    0.30%    Panthenol DL               0.225%    Pantyl Ethyl Ether         0.025%    Main Mix    Water                     66.02%    Hydrophobically Modified Hydroxyethylcellulose.sup. 2!                              1.23%    Xanthan Gum               0.25%    Citric Acid               0.02%    Sodium Citrate            0.09%    Cetyl Alcohol             0.12%    Stearyl Alcohol           0.08%    Polymer-Solvent component Mixture    Copolymer 1.sup. 3!       2.00%    Cyclomethicone D4         5.00%    Hexamethyl disiloxane     5.00%    Dimethylmyristamine (ARMEENDM14D).sup. 4!                              1.33%    Methylchloroisothiazolinone Methylisothiazolinone                              0.03%    Perfume                   0.33%    Benzyl Alcohol            0.50%    ______________________________________     .sup. 1! Dimethicone Gum in D5 cyclomethicone; commercially available fro     GE     .sup. 2! Polysurf 67 ® supplied by Aqualon     .sup. 3! Poly (tbutyl acrylate)(acrylic acid)graft-polydimethylsiloxane)     .sup. 4! Commercially available from Akzo

This product is prepared by dispersing the copolymer in thecyclomethicone D4 and hexamethyl disiloxane (solvent component) thenadding the dimethylmyristamine. Heat the solution to 65° C. and use anappropriate homogenizer to facilitate incorporation of the copolymerinto the solvent component. Premixes A and B are prepared by combiningmaterials at 70° C. Premix A goes through a colloid mill and is cooledto 38° C. Materials in `Main Mix`, except benzyl alcohol, are mixed at65° C. The polymer solution is then added to the `Main Mix`. Main mixgoes through a colloid mill and is cooled to 38° C. Premixes and kin Mixare combined at 38° C. Then the benzyl alcohol is added. Thiscomposition is useful for application to the hair to provideconditioning, styling and hold benefits.

Example 14

The following is a hair styling mousse composition representative of thepresent invention.

    ______________________________________    Component             Weight %    ______________________________________    Water                 Q.S. to 100%    Tallowtrimonium Chloride                          0.10%    Hydrogenated Ditallowdimonium Chloride                          0.90%    (Quaternium 18)    Lauramine Oxide       0.20%    Panthenol             0.05%    Perfume               0.20%    Copolymer 1.sup. 1!   1.00%    lauramine             0.51%    Hexamethyl disiloxane 3.00%    Isobutane             7.00%    ______________________________________     .sup. 1! Polyt(tbutyl acrylate)(acrylic acid)graft-polydiethylsiloxane)

This product is prepared by dispersing the copolymer in hexamethyldisiloxane (solvent component) then adding the lauramine. Heat thesolution to 65° C. and use an appropriate homogenizer to facilitateincorporation of the copolymer into the solvent component. The othercomponents (except isobutane) are mixed in a separate vessel at atemperature high enough (70° C.) to melt the solids. The polymer/solventcomponent solution is added to the other components after those havebeen cooled. Aluminum aerosol cans are then filled with 93 parts of thisbatch, affixed with a valve which is crimped into position, and lastlypressure filled with 7 parts Isobutane. This composition is useful forapplication to the hair to provide conditioning, styling and holdbenefits.

Example 15

The following is a hair styling spray composition representative of thepresent invention.

    ______________________________________    Component        Weight %    ______________________________________    Water            Q.S. to 100%    Panthenol        0.05%    Perfume          0.20%    Copolymer 4.sup. 1!                     2.00%    Dimethylmyristamine                     1.33%    Cyclomethicone D4                     7.00%    Isobutane        25.00%    ______________________________________     .sup. 1! poly (tbutyl acrylate)(acrylic acid)graft-polyisobutylene)

This product is prepared by dispersing the copolymer in CyclomethiconeD4 (solvent component) then adding the dimethylmyristamine. Heat thesolution to 65° C. and use an appropriate homogenizer to facilitateincorporation of the copolymer into the solvent component. The othercomponents (except isobutane) are mixed in a separate vessel. Thepolymer/solvent component solution is added to the other components.Aluminum aerosol cans are then filled with 75 parts of this batch,affixed with a valve which is crimped into position, and lastly pressurefilled with 25 parts Isobutane. This composition is useful forapplication to the hair to provide conditioning, styling and holdbenefits

When the compositions defined in Examples 4-12 are applied to hair inthe conventional manner, they provide effective hair conditioning andstyling/hold benefits without leaving the hair with a sticky/stiff feel.

Example 16

The following is a hair styling rinse composition representative of thepresent invention.

    ______________________________________    Component                 Weight %    ______________________________________    Premix A    Water                     8.14%    Ditallowdimonium Chloride (Varisoft 470)                              1.43%    CF1213 ® (Dimethicone Gum) 2!                              2.33%    Amodimethicone            0.10%    Premix B    Water                     5.45%    Stearalkonium Chloride    0.30%    Panthenol DL               0.225%    Pantyl Ethyl Ether         0.025%    Main Mix    Water                     71.35%    Hydrophobically Modified Hydroxyethylcellulose 1!                              1.23%    Xanthan Gum               0.25%    Citric Acid               0.02%    Sodium Citrate            0.09%    Cetyl Alcohol             0.12%    Stearyl Alcohol           0.08%    Polymer-Solvent Mixture    Copolymer #1              2.00%    Cyclomethicone D4         4.67%    Dimethylmyristamine (ARMEENDM14D)                              1.33%    Methylchloroisothiazolinone Methylisothiazolinone                              0.03%    Perfume                   0.33%    Benzyl Alcohol            0.50%    ______________________________________      1!Polysurf 67 ® supplied by Aqualon      2!Commercially available from GE

This product is prepared by dispersing the copolymer #1 in thecyclomethicone D4(solvent) then adding the dimethylmyristamine. Heat thesolution to 65 C. and use an appropriate homogenizer to facilitateincorporation of the copolymer into the solvent. Premixes A and B areprepared by combining materials at 70° C. Premix A goes through acolloid mill and is cooled to 38° C. Materials in `Main Mix`, exceptbenzyl alcohol, are mixed at 65° C. The polymer solution is then addedto the `Main Mix`. Main mix goes through a colloid mill and is cooled to38° C. Premixes and Main Mix are combined at 38° C. Then the benzylalcohol is added. This composition is useful for application to the hairto provide conditioning, styling and hold benefits.

Example 17

The following is a hair styling rinse composition representative of thepresent invention.

    ______________________________________    Component                 Weight %    ______________________________________    Premix A    Water                     8.14%    Ditallowdimonium Chloride (Varisoft 470)                              1.43%    CF1213 ® (Dimethicone Gum) 2!                              2.33%    Amodimethicone            0.10%    Premix B    Water                     5.45%    Stearalkonium Chloride    0.30%    Panthenol DL               0.225%    Pantyl Ethyl Ether         0.025%    Main Mix    Water                     70.46%    Hydrophobically Modified Hydroxyethylcellulose 1!                              1.23%    Xanthan Gum               0.25%    Citric Acid               0.02%    Sodium Citrate            0.09%    Cetyl Alcohol             0.12%    Stearyl Alcohol           0.08%    Polymer-Solvent Mixture    Copolymer #1              2.00%    Cyclomethicone D4         5.56%    Dimethylmyristamine (ARMEENDM14D)                              1.33%    Methylchloroisothiazolinone Methylisothiazolinone                              0.03%    Perfume                   0.33%    Benzyl Alcohol            0.50%    ______________________________________      1!Polysurf 67 ® supplied by Aqualon      2!Commercially available from GE

This product is prepared by dispersing the copolymer #1 in thecyclomethicone D4(solvent) then adding the dimethylmyristamine. Heat thesolution to 65 C. and use an appropriate homogenizer to facilitateincorporation of the copolymer into the solvent. Premixes A and B areprepared by combining materials at 70° C. Premix A goes through acolloid mill and is cooled to 38° C. Materials in `Main Mix`, exceptbenzyl alcohol, are mixed at 65° C. The polymer solution is then addedto the `Main Mix`. Main mix goes through a colloid mill and is cooled to38° C. Premixes and `Main Mix` are combined at 38° C. Then the benzylalcohol is added. This composition is useful for application to the hairto provide conditioning, styling and hold benefits.

Example 18

The following is a hair styling rinse composition representative of thepresent invention.

    ______________________________________    Component                 Weight %    ______________________________________    Premix A    Water                     8.14%    Ditallowdimonium Chloride (Varisoft 470)                              1.43%    CF1213 ® (Dimethicone Gum) 2!                              2.33%    Amodimethicone            0.10%    Premix B    Water                     5.45%    Stearalkonium Chloride    0.30%    Panthenol DL               0.225%    Pantyl Ethyl Ether         0.025%    Main Mix    Water                     72.08%    Hydrophobically Modified Hydroxyethylcellulose 1!                              1.23%    Xanthan Gum               0.25%    Citric Acid               0.02%    Sodium Citrate            0.09%    Cetyl Alcohol             0.12%    Stearyl Alcohol           0.08%    Polymer-Solvent Mixture    Copolymer #1              2.00%    Isododecane               4.09%    Dimethyllauramine (ARMEENDM12D)                              1.18%    Methylchloroisothiazolinone Methylisothiazolinone                              0.03%    Perfume                   0.33%    Benzyl Alcohol            0.50%    ______________________________________      1!Polysurf 67 ® supplied by Aqualon      2!Commercially available from GE

This product is prepared by dispersing the copolymer #1 in thecyclomethicone D4(solvent) then adding the dimethylmyristamine. Heat thesolution to 65 C. and use an appropriate homogenizer to facilitateincorporation of the copolymer into the solvent. Premixes A and B areprepared by combining materials at 70° C. Premix A goes through acolloid mill and is cooled to 38° C. Materials in `Main Mix`, exceptbenzyl alcohol, are mixed at 65° C. The polymer solution is then addedto the `Main Mix`. Main mix goes through a colloid mill and is cooled to38° C. Premixes and kin Mix are combined at 38° C. Then the benzylalcohol is added. This composition is useful for application to the hairto provide conditioning, styling and hold benefits.

Example 19

The following is a sunscreen composition representative of the presentinvention.

An oil-in-water emulsion is prepared by combining the followingcomponents utilizing conventional mixing techniques.

    ______________________________________    Ingredients               Weight %    ______________________________________    Phase A    Water                     QS100    Carbomer 954.sup. 1!      0.24    Carbomer 1342.sup. 2!     0.16    Disodium EDTA             0.05    Phase B    Isoarachidyl Neopentanoate.sup. 3!                              2.00    PVP Eicosene Copolymer.sup. 4!                              2.00    Octyl Methoxycinnamate    7.50    Octocrylene               4.00    Oxybenzone                1.00    Titanium Dioxide          2.00    Cetyl Palmitate           0.75    Stearoxytrimethylsilane (and)                              0.50    Stearyl Alcohol.sup. 5!    Glyceryl Tribehenate      0.75    Dimethicone               1.00    Tocopheryl Acetate        0.10    DEA-Cetyl Phosphate       0.20    Phase C    Water                     2.00    Triethanolamine 99%       0.60    Phase D    Water                     2.00    Butylene Glycol           2.00    DMDM Hydantoin (and) Iodopropynyl Butylcarbamate.sup. 6!                              0.25    dL Panthenol              1.00    Phase E    Cyclomethicone D4         4.00    Copolymer 6.sup. 7!       1.00    stearamine                1.25    ______________________________________     .sup. 1! Available as Carbopol ® 954 from B.F. Goodrich.     .sup. 2! Available as Carbopol ® 1342 from B.F. Goodrich.     .sup. 3! Available as Ganex V220 from GAF Corporation.     .sup. 4! Available as DC 580 Wax from Dow Corning.     .sup. 5! Available as Synchrowax HRC from Croda.     .sup. 6! Available as Glydant Plus from Lonza.     .sup. 7! Poly (tbutyl acrylate)(methacrylic     acid)(2-ethylhexylmethacrylate)

In a suitable vessel the Phase A ingredients are dispersed in the waterand heated to 75°-85° C. In a separate vessel the Phase B ingredients(except DEA-Cetyl Phosphate) are combined and heated to 85°-90° C. untilmelted. Next, the DEA-Cetyl Phosphate is added to the liquid Phase B andstirred until dissolved. This mixture is then added to Phase A to formthe emulsion. The Phase C ingredients are combined until dissolved andthen added to the emulsion. The emulsion is then cooled to 40°-45° C.with continued mixing. In another vessel, the Phase D ingredients areheated with mixing to 40°-45° C. until a clear solution is formed andthis solution is then added to the emulsion. The emulsion is cooled to35° C. The Phase E ingredients are combined at 65° C., use anappropriate homogenizer to facilitate incorporation of the copolymerinto the solvent component. Phase E is the cooled to 35° C., added andmixed.

This emulsion is useful for topical application to the skin to provideprotection from the harmful effects of ultraviolet radiation.

Example 20

The following is a facial moisturizing composition representative of thepresent invention.

A leave-on facial emulsion composition containing a cationic hydrophobicsurfactant is prepared by combining the following components utilizingconventional mixing techniques.

    ______________________________________    Ingredient                 Weight %    ______________________________________    Phase A    Water                      QS100    Glycerin                   3.00    Cetyl Palmitate            3.00    Cetyl Alcohol              1.26    Quaternium-22              1.00    Glyceryl Monohydroxy Stearate                               0.74    Dimethicone                0.60    Stearic Acid               0.55    Octyldodecyl Myristate     0.30    Potassium Hydroxide        0.20    Carbomer 1342              0.125    Tetrasodium EDTA           0.10    DMDM Hydantoin and Iodopropynyl Butyl Carbamate                               0.10    Carbomer 951               0.075    Phase B    Isododecane               4.00    Copolymer 2.sup. 1!       1.00    stearamine                0.31    ______________________________________     .sup. 1! Poly (tbutyl acrylate)(methacrylic     acid)graft-polydimethylsiloxane)

In a suitable vessel the Phase A ingredients are combined to form anemulsion. Phase B is prepared by dispersing the copolymer in Isododecane(solvent component) then adding the stearamine. Heat the solution to 65°C. and use an appropriate homogenizer to facilitate incorporation of thecopolymer into the solvent component Cool the Phase B and mix into PhaseA using conventional mixing techniques.

This emulsion is useful for application to the skin as a moisturizer.

Example 21

The following is an antiperspirant composition representative of thepresent invention.

    ______________________________________    Component            Weight %    ______________________________________    PPG 2 Myristyl Propionate                         34.00%    Glyceryl C.sub.18 -C.sub.36 Wax Acid Ester                         0.40%    Cyclomethicone       32.75%    Copolymer 1.sup. 1!  1.00%    Dimethylmyristamine  0.67%    Aluminum Chlorohydrate                         19.00%    PPG 5 Ceteth 20      7.50%    Water                1.50%    ______________________________________     .sup. 1! Poly(tbutyl acrylate)(acrylic acid)graft-polydimethylsiloxane)

Mix PPG 2 Myristyl Propionate and Glyceryl C₁₈ -C₃₆ Wax Acid Ester, heatto 75° C. Disperse the Chlorohydrate. Disperse the copolymer inCyclomethicone (solvent component) then add the dimethylmyristamine.Heat the solution to 65° C. and use an appropriate homogenizer tofacilitate incorporation of the copolymer into the solvent component.Add the cyclomethicone mixture to the Chlorohydrate dispersion. Mix PPG5 Ceteth 20 and the water, the add to oils, perfume and cool.

Example 22

The following is an anti-acne composition representative of the presentinvention.

    ______________________________________    Component        Weight %    ______________________________________    Copolymer-Solvent component Mix    Copolymer 5.sup. 1!                     1.00%    dimethylpalmitamine                     0.31%    Isopar H ®.sup. 2!                     3.75%    Main Mix    Water            Q.S. to 100%    Ethanol (SDA 40) 40.00%    Carbopol 940 ®                     0.75%    Triethanol Amine 1.00%    Salicylic Acid   2.00%    ______________________________________     .sup. 1! Poly (tbutyl acrylate)(methacrylic acid)graft-polyisobutylene)     .sup. 2! C.sub.11 -C.sub.12 Isoparaffin, available from Exxon Chemical Co

This product is prepared by dispersing the copolymer in Isopar H®(solvent component) then adding the dimethylpalmitamine. Heat thesolution to 65° C. and use an appropriate homogenizer to facilitateincorporation of the copolymer into the solvent component. The othercomponents are mixed in a separate vessel at ambient temperature. Thecopolymer-solvent component premix is cooled (if needed) and added tothe other components. This composition is useful for application to theskin to provide improve water resistance and is useful in the treatmentof acne.

Example 23

The following is a topical analgesic composition representative of thepresent invention.

    ______________________________________    Component        Weight %    ______________________________________    Copolymer-Solvent component Mix    Copolymer 1.sup. 1!                     1.00%    dimethylpalmitamine                     0.74%    Isopar H ®.sup. 2!                     3.75%    Main Mix    Water            Q.S. to 100%    Ethanol (SDA 40) 20.00%    Carbopol 940 ®                     0.75%    Triethanol Amine 1.00%    Ibuprofen        2.00%    ______________________________________     .sup. 1! Poly (tbutyl acrylate)(acrylic acid)graft-polydimethylsiloxane)     .sup. 2! C.sub.11 -C.sub.12 Isoparaffin, available from Exxon Chemical Co

This product is prepared by dispersing the copolymer in Isopar H®(solvent component) then adding the dimethylpalmitamine. Heat thesolution to 65° C. and use an appropriate homogenizer to facilitateincorporation of the copolymer into the solvent component. The othercomponents are mixed in a separate vessel at ambient temperature. Thecopolymer-solvent component premix is cooled (if needed) and added tothe other components. This composition is useful for application to theskin to provide improve water resistance and is useful for the analgesiceffects.

What is claimed is:
 1. A personal care composition, comprising:A.) acopolymer complex comprising:a.) a copolymer having a backbone formedfrom the copolymerization of repeating A monomer and B monomer unitswherein the backbone has optionally grafted to it hydrophobic Cmacromonomer units wherein the copolymer is prepared by thepolymerization combination of the following relative weight percentagesof the A, B, and C units:i) from about 10% to about 99% by weight of thecopolymer of one or more hydrophobic A monomer units selected from thegroup consisting of t-butyl acrylate, t-butyl methacrylate, t-butylstyrene, 2-ethylhexyl methacrylate and mixtures thereof, wherein the Amonomer units are copolymerizable with the B monomer and C macromonomerunits; ii) from about 1% to about 40% by weight of the copolymer of oneor more hydrophilic B monomer units selected from the group consistingof acrylic acid, methacrylic acid, N,N-dimethyl acrylamide, t-butylacrylamide, vinyl pyrrolidone, and mixtures thereof, wherein the Bmonomer units are copolymerizable with the A monomer and C macromonomerunits and iii) from about 5% to about 40% by weight of the copolymer ofone or more C macromonomer units selected from the group of polymersconsisting of poly(n-butyl acrylate), poly(dodecyl acrylate),poly(2-ethylhexyl acrylate), poly(2-ethylbutyl acrylate), poly(n-ethylacrylate), poly(n-heptyl acrylate), poly(n-hexyl acrylate),poly(iso-butyl acrylate), poly(iso-decyl acrylate, poly(iso-propylacrylate), poly(3-methylbutyl acrylate), poly(2-methylpentyl acrylate),poly(nonyl acrylate), poly(octyl acrylate), poly(propyl acrylate), poly(2-ethylhexyl methacrylate), poly(tridecyl methacrylate), poly (hexylmethacrylate), poly(decyl methacrylate), poly(octyl methacrylate),poly(octadecyl methacrylate), poly(dodecyl methacrylate), poly(n-pentylmethacrylate), poly(isobutylene), poly(isoprene), hydrogenatedpoly(1,2-butadiene), hydrogenated poly(1,4-butadiene), hydrogenatedpoly(isoprene), poly(1,2-butadiene), poly(1-butene),poly(5-methyl-1-hexene), poly(6-methyl-1-heptene),poly(4,4-dimethyl-1-pentene), poly(iso-butyl vinyl ether),poly(4-t-butyl vinyl benzene-co-2-ethylhexyl acrylate),poly(2-ethylhexyl acrylate-co-octyl acrylamide), poly(2-ethyl vinylbenzene-co-octyl methacrylate), and mixtures thereof wherein thepolymers are endcapped by an endcapping group selected from the groupconsisting of acryloyl, methacryloyl, 2-vinylbenzyl, 3-vinylbenzyl, and4-vinylbenzyl, wherein the C units are hydrophobic macromonomer units,copolymerizable with the A monomer units and the B monomer units, the Cmacromonomer units having a number average molecular weight of fromabout 1,500 to about 50,000; and b.) a complexing fatty amine whereinthe fatty amine is selected from the group consisting of C₁ -C₂₂ primaryamines, C₁ -C₂₂ secondary amines and C₁ -C₂₂ tertiary amines, C₁ -C₂₂quaternary ammonium salts, C₁ -C₂₂ polyamines, alkyl substitutedheterocyclic amines selected from the group consisting of aminoethylhexadecylimidazoline, N-ethyl morpholine, and N-ethyl piperidine andmixtures thereof, salts thereof and mixtures thereof and wherein thefatty amine forms a complex with the acid functional B monomer unitswherein the weight ratio of the copolymer to the fatty amine is fromabout 50:1 to about 1:1; and B.) a volatile, hydrophobic solventcomponent for the copolymer complex having a boiling point at 1atmosphere of about 260° C. or less and a solubility parameter of about8.5 (cal/cm³)^(1/2) or less wherein the copolymer complex is soluble ordispersible in the volatile, hydrophobic solvent component.
 2. Apersonal care composition according to claim 1, wherein the complexingfatty amine is a tertiary amine or salt thereof having the formula R¹ R²R³ N wherein R¹, R² and R³ are independently selected from the groupconsisting of C₁ -C₂₂ straight chain aliphatic, C₂ -C₂₂ hydroxyalkyl, C₂-C₂₂ amidoalkyl, C₂ -C₂₂ carboxyalkyl, C₃ -C₂₂ cyclic, C₂ -C₂₂ alkoxy,C₂ -C₂₂ polyalkoxy, and C₂ -C₂₂ hydroxypolyalkoxy groups and C₁ -C₂₂branched chained aliphatic, C₂ -C₂₂ hydroxyalkyl, C₂ -C₂₂ amidoalkyl, C₂-C₂₂ carboxyalkyl, C₃ -C₂₂ cyclic, C₂ -C₂₂ alkoxy, C₂ -C₂₂ polyalkoxy,and C₂ -C₂₂ hydroxypolyalkoxy groups and mixtures thereof.
 3. A personalcare composition according to claim 1, wherein the complexing fattyamine is a tertiary amine or salt thereof having the formula R¹ R² R³ Nwherein R¹ is selected from the group consisting of C₁₀ -C₁₈ straightchain aliphatic, C₁₀ -C₁₈ hydroxyalkyl, C₁₀ -C₁₈ amidoalkyl, C₁₀ -C₁₈carboxyalkyl, C₁₀ -C₁₈ cyclic, C₁₀ -C₁₈ alkoxy, C₁₀ -C₁₈ polyalkoxy, C₁₀-C₁₈ hydroxypolyalkoxy groups C₁₀ -C₁₈ branched chained aliphatic, C₁₀-C₁₈ hydroxyalkyl, C₁₀ -C₁₈ amidoalkyl, C₁₀ -C₁₈ carboxyalkyl, C₁₀ -C₁₈cyclic, C₁₀ -C₁₈ alkoxy, C₁₀ -C₁₈ polyalkoxy, and C₁₀ -C₁₈hydroxypolyalkoxy groups provided R² is a methyl group and R³ ═R².
 4. Apersonal care composition according to claim 3, wherein the copolymer ofthe copolymer complex is prepared by the polymerization combination ofthe following relative weight percentages of said A, B and C units:a.from about 40% to about 80% of said hydrophobic A unit; b. from 5% toabout 30% of said hydrophilic B unit; and c. from about 5% to about 40%of said hydrophobic C unit wherein said C unit has a number averagemolecular weight of from about 5,000 to about 30,000.
 5. A personal carecomposition according to claim 4, wherein said volatile, hydrophobicsolvent component is selected from the group consisting of hydrophobic,volatile C₇ -C₁₄ branched hydrocarbons, hydrophobic, volatile siliconesand mixtures thereof.
 6. A personal care composition according to claim5, wherein said volatile, hydrophobic solvent component is selected fromthe group consisting of hexamethyl disiloxane, isododecane,cyclomethicone and mixtures thereof.
 7. A personal care compositionaccording to claim 6, further comprising a carrier selected from thegroup consisting of mousses, gels, lotions, creams, ointments, tonics,sprays, aerosols, shampoos, conditioners, rinses, bar soaps, handlotions body lotions, facial moisturizers, and solid gel sticks.
 8. Apersonal care composition according to claim 7, wherein said compositionfurther comprising from about 10% to about 30% by weight of thecomposition of a synthetic surfactant.
 9. A personal care compositionaccording to claim 8, wherein said synthetic surfactant is selected fromthe group consisting of alkyl sulfates, ethoxylated alkyl sulfates, andmixtures thereof.
 10. A personal care composition according to claim 9,wherein the composition is a shampoo.
 11. A personal care compositionaccording to claim 7, wherein said composition further comprises apharmaceutical active selected from the group consisting of antiacneactives, analgesic actives, antipruritic actives, anesthetic actives,antimicrobial actives, sunscreen actives, sunless tanning actives,skin-bleaching actives, anti-dandruff actives, antiperspirant actives,deodorant actives and mixtures thereof.
 12. A personal care composition,comprising:A.) a copolymer complex comprising:a.) a copolymer having abackbone formed from the copolymerization of repeating A monomer and Bmonomer units wherein the backbone has optionally grafted to ithydrophobic C macromonomer units wherein the copolymer is prepared bythe polymerization combination of the following relative weightpercentages of the A, B, and C units:i) from about 10% to about 99% byweight of the copolymer of one or more hydrophobic A monomer unitsselected from the group consisting of t-butyl acrylate, t-butylmethacrylate, t-butyl styrene, 2-ethylhexyl methacrylate and mixturesthereof, wherein the A monomer units are copolymerizable with the Bmonomer and C macromonomer units; ii) from about 1% to about 40% byweight of the copolymer of one or more hydrophilic B monomer unitsselected from the group consisting of acrylic acid, methacrylic acid,N,N-dimethyl acrylamide, t-butyl acrylamide, vinyl pyrrolidone, andmixtures thereof, wherein the B monomer units are copolymerizable withthe A monomer and C macromonomer units andiii) from about 5% to 40% byweight of the copolymer of one or more C macromonomer units selectedfrom the group of polymers consisting of poly(n-butyl acrylate),poly(dodecyl acrylate), poly(2-ethylhexyl acrylate), poly(2-ethylbutylacrylate), poly(n-ethyl acrylate), poly(n-heptyl acrylate), poly(n-hexylacrylate), poly(iso-butyl acrylate), poly(iso-decyl acrylate,poly(iso-propyl acrylate), poly(3-methylbutyl acrylate),poly(2-methylpentyl acrylate), poly(nonyl acrylate), poly(octylacrylate), poly(propyl acrylate), poly(2-ethylhexyl methacrylate),poly(tridecyl methacrylate), poly(hexyl methacrylate), poly(decylmethacrylate), poly(octyl methacrylate), poly(octadecyl methacrylate),poly(dodecyl methacrylate), poly(n-pentyl methacrylate),poly(isobutylene), poly(isoprene), hydrogenated poly(1,2-butadiene),hydrogenated poly(1,4-butadiene), hydrogenated poly(isoprene),poly(1,2-butadiene), poly(1-butene), poly(5-methyl-1-hexene),poly(6-methyl-1-heptene), poly(4,4-dimethyl-1-pentene), poly(iso-butylvinyl ether), poly(4-t-butyl vinyl benzene-co-2-ethylhexyl acrylate),poly(2-ethylhexyl acrylate-co-octyl acrylamide), poly(2-ethyl vinylbenzene-co-octyl methacrylate), and mixtures thereof wherein thepolymers are endcapped by an endcapping group selected from the groupconsisting of acryloyl, methacryloyl, 2-vinylbenzyl, 3-vinylbenzyl, and4-vinylbenzyl, wherein the C units are hydrophobic macromonomer units,copolymerizable with the A monomer units and the B monomer units, the Cmacromonomer units having a number average molecular weight of fromabout 1,500 to about 50,000; and b.) a complexing fatty amine whereinthe fatty amine is selected from the group consisting of C₁ -C₂₂ primaryamines, C₁ -C₂₂ secondary amines and C₁ -C₂₂ tertiary amines, C₁ -C₂₂quaternary ammonium salts, C₁ -C₂₂ polyamines, alkyl substitutedheterocyclic amines selected from the group consisting of aminoethylhexadecylimidazoline, N-ethyl morpholine, and N-ethyl piperidine andmixtures thereof, salts thereof and mixtures thereof and wherein thefatty amine forms a complex with the acid functional B monomer unitswherein the weight ratio of the copolymer to the fatty amine is fromabout 50:1 to about 1:1; and B.) a volatile, hydrophobic solventcomponent for the copolymer complex having a boiling point at 1atmosphere of about 260° C. or less and a solubility parameter of about8.5 (cal/cm³)^(1/2) or less; and C.) a carrier immiscible with thevolatile hydrophobic solvent component wherein the copolymer complex issoluble or dispersible in the volatile, hydrophobic solvent component.13. A method of treating hair by administering a safe and effectiveamount of the compositions according to claim
 1. 14. A method oftreating skin by administering a safe and effective amount of thecompositions according to claim
 1. 15. A method of making a personalcare composition, comprising the steps of:a.) preparing a copolymerhaving a backbone formed from the copolymerization of repeating Amonomer and B monomer units wherein the backbone has optionally graftedto it hydrophobic C macromonomer units wherein the copolymer is preparedby the polymerization combination of the following relative weightpercentages of the A, B, and C units:i) from about 10% to about 99% byweight of the copolymer of one or more hydrophobic A monomer unitsselected from the group consisting of t-butyl acrylate, t-butylmethacrylate, t-butyl styrene, 2-ethylhexyl methacrylate and mixturesthereof, wherein the A monomer units are copolymerizable with the Bmonomer and C macromonomer units; ii) from about 1% to about 40% byweight of the copolymer of one or more hydrophilic B monomer unitsselected from the group consisting of acrylic acid, methacrylic acid,N,N-dimethyl acrylamide, t-butyl acrylamide, vinyl pyrrolidone, andmixtures thereof, wherein the B monomer units are copolymerizable withthe A monomer and C macromonomer units and iii) from about 5% to about40% by weight of the copolymer of one or more C macromonomer unitsselected from the group of polymers consisting of poly(n-butylacrylate), poly(dodecyl acrylate), poly(2-ethylhexyl acrylate),poly(2-ethylbutyl acrylate), poly(n-ethyl acrylate), poly(n-heptylacrylate), poly(n-hexyl acrylate), poly(iso-butyl acrylate),poly(iso-decyl acrylate, poly(iso-propyl acrylate), poly(3-methylbutylacrylate), poly(2-methylpentyl acrylate), poly(nonyl acrylate),poly(octyl acrylate), poly(propyl acrylate), poly (2-ethylhexylmethacrylate), poly(tridecyl methacrylate), poly (hexyl methacrylate),poly(decyl methacrylate), poly(octyl methacrylate), poly(octadecylmethacrylate), poly(dodecyl methacrylate), poly(n-pentyl methacrylate),poly(isobutylene), poly(isoprene), hydrogenated poly(1,2-butadiene),hydrogenated poly(1,4 butadiene), hydrogenated poly(isoprene),poly(1,2-butadiene), poly(1-butene), poly(5-methyl-1-hexene),poly(6-methyl-1-heptene), poly(4,4-dimethyl-1-pentene), poly(iso-butylvinyl ether), poly(4-t-butyl vinyl benzene-co-2-ethylhexyl acrylate),poly(2-ethylhexyl acrylate-co-octyl acrylamide), poly(2-ethyl vinylbenzene-co-octyl methacrylate), and mixtures thereof wherein thepolymers are endcapped by an endcapping group selected from the groupconsisting of acryloyl, methacryloyl, 2-vinylbenzyl, 3-vinylbenzyl, and4-vinylbenzyl, wherein the C units are hydrophobic macromonomer units,copolymerizable with the A monomer units and the B monomer units, the Cmacromonomer units having a number average molecular weight of fromabout 1,500 to about 50,000; b.) complexing the copolymer with a fattyamine wherein the fatty amine is selected from the group consisting ofC₁ -C₂₂ primary amines, C₁ -C₂₂ secondary amities and C₁ -C₂₂ tertiaryamines, C₁ -C₂₂ quaternary ammonium salts, C₁ -C₂₂ polyamines, alkylsubstituted heterocyclic amines selected from the group consisting ofaminoethyl hexadecylimidazoline, N-ethyl morpholine, and N-ethylpiperidine and mixtures thereof, salts thereof and mixtures thereof andwherein the fatty amine forms a complex with the acid functional Bmonomer units and wherein the weight ratio of the copolymer to the fattyamino is from about 50:1 to about 1:1; and c.) dissolving or dispersingthe copolymer complex in a volatile, hydrophobic solvent componenthaving a boiling point at 1 atmosphere of about 260° C. or less and asolubility parameter of about 8.5 (cal/cm³)^(1/2) or less.
 16. Apersonal care composition which prior to mixing, comprises:A.) acopolymer complex comprising:a.) a copolymer having a backbone formedfrom the copolymerization of repeating A monomer and B monomer unitswherein the backbone has optionally grafted to it hydrophobic Cmacromonomer units wherein the copolymer is prepared by thepolymerization combination of the following relative weight percentagesof the A, B, and C units:i) from about 10% to about 99% by weight of thecopolymer of one or more hydrophobic A monomer units selected from thegroup consisting of t-butyl acrylate, t-butyl methacrylate, t-butylstyrene, 2-ethylhexyl methacrylate and mixtures thereof, wherein the Amonomer units are copolymerizable with the B monomer and C macromonomerunits; ii) from about 1% to about 40% by weight of the copolymer of oneor more hydrophilic B monomer units selected from the group consistingof acrylic acid, methacrylic acid, N,N-dimethyl acrylamide, t-butylacrylamide, vinyl pyrrolidone, and mixtures thereof, wherein the Bmonomer units are copolymerizable with the A monomer and C macromonomerunits; and iii) from about 5% to about 40% by weight of the copolymer ofone or more C macromonomer units selected from the group of polymersconsisting of poly(n-butyl acrylate), poly(dodecyl acrylate),poly(2-ethylhexyl acrylate), poly(2-ethylbutyl acrylate), poly(n-ethylacrylate), poly(n-heptyl acrylate), poly(n-hexyl acrylate),poly(iso-butyl acrylate), poly(iso-decyl acrylate, poly(iso-propylacrylate), poly(3-methylbutyl acrylate), poly(2-methylpentyl acrylate),poly(nonyl acrylate), poly(octyl acrylate), poly(propyl acrylate), poly(2-ethylhexyl methacrylate), poly(tridecyl methacrylate), poly (hexylmethacrylate), poly(decyl methacrylate), poly(octyl methacrylate),poly(octadecyl methacrylate), poly(dodecyl methacrylate), poly(n-pentylmethacrylate), poly(isobutylene), poly(isoprene), hydrogenatedpoly(1,2-butadiene), hydrogenated poly(1,4-butadiene), hydrogenatedpoly(isoprene), poly(1,2-butadiene), poly(1-butene),poly(5-methyl-1-hexene), poly(6-methyl-1-heptene),poly(4,4-dimethyl-1-pentene), poly(iso-butyl vinyl ether),poly(4-t-butyl vinyl benzene-co-2-ethylhexyl acrylate),poly(2-ethylhexyl acrylate-co-octyl acrylamide), poly(2-ethyl vinylbenzene-co-octyl methacrylate), and mixtures thereof wherein thepolymers are endcapped by an endcapping group selected from the groupconsisting of acryloyl, methacryloyl, 2-vinylbenzyl, 3-vinylbenzyl, and4-vinylbenzyl, wherein the C units are hydrophobic macromonomer units,copolymerizable with the A monomer units and the B monomer units, the Cmacromonomer units having a number average molecular weight of fromabout 1,500 to about 50,000; and b.) a complexing fatty amine whereinthe fatty amine is selected from the group consisting of C₁ -C₂₂ primaryamines, C₁ -C₂₂ secondary amines and C₁ -C₂₂ tertiary amines, C₁ -C₂₂quaternary ammonium salts, C₁ -C₂₂ polyamines, alkyl substitutedheterocyclic amines selected from the group consisting of aminoethylhexadecylimidazoline, N-ethyl morpholine, and N-ethyl piperidine andmixtures thereof, salts thereof and mixtures thereof and wherein thefatty amine forms a complex with the acid functional B monomer unitswherein the weight ratio of the copolymer to the fatty amine is fromabout 50:1 to about 1:1; and B.) a volatile, hydrophobic solventcomponent for the copolymer complex having a boiling point at 1atmosphere of about 260° C. or less and a solubility parameter of about8.5 (cal/cm³)^(1/2) or less wherein the copolymer complex is soluble ordispersible in the volatile, hydrophobic solvent component.
 17. A hairstyling and conditioning composition, comprising:A.) a copolymer complexcomprising:a.) a copolymer having a backbone formed from thecopolymerization of repeating A monomer and B monomer units wherein thebackbone has optionally grafted to it hydrophobic C macromonomer unitswherein the copolymer is prepared by the polymerization combination ofthe following relative weight percentages of the A, B, and C units:i)from about 10% to about 99% by weight of the copolymer of one or morehydrophobic A monomer units selected from the group consisting oft-butyl acrylate, t-butyl methacrylate, t-butyl styrene, 2-ethylhexylmethacrylate and mixtures thereof, wherein the A monomer units arecopolymerizable with the B monomer and C macromonomer units; ii) fromabout 1% to about 40% by weight of the copolymer of one or morehydrophilic B monomer units selected from the group consisting ofacrylic acid, methacrylic acid, N,N-dimethyl acrylamide, t-butylacrylamide, vinyl pyrrolidone, and mixtures thereof, wherein the Bmonomer units are copolymerizable with the A monomer and C macromonomerunits andiii) from about 5% to about 40% by weight of the copolymer ofone or more C macromonomer units selected from the group of polymersconsisting of poly(n-butyl acrylate), poly(dodecyl acrylate),poly(2-ethylhexyl acrylate), poly(2-ethylbutyl acrylate), poly(n-ethylacrylate), poly(n-heptyl acrylate), poly(n-hexyl acrylate),poly(iso-butyl acrylate), poly(iso-decyl acrylate, poly(iso-propylacrylate), poly(3-methylbutyl acrylate), poly(2-methylpentyl acrylate),poly(nonyl acrylate), poly(octyl acrylate), poly(propyl acrylate), poly(2-ethylhexyl methacrylate), poly(tridecyl methacrylate), poly (hexylmethacrylate), poly(decyl methacrylate), poly(octyl methacrylate),poly(decyl methacrylate), poly(dodecyl methacrylate), poly(n-pentylmethacrylate), poly(isobutylene), poly(isoprene), hydrogenatedpoly(1,2-butadiene), hydrogenated poly(1,4-butadiene), hydrogenatedpoly(isoprene), poly(1,2-butadiene), poly(1-butene),poly(5-methyl-1-hexene), poly(6-methyl-1-heptene),poly(4,4-dimethyl-1-pentene), poly(iso-butyl vinyl ether),poly(4-t-butyl vinyl benzene-co-2-ethylhexyl acrylate),poly(2-ethylhexyl acrylate-co-octyl acrylamide), poly(2-ethyl vinylbenzene-co-octyl methacrylate), and mixtures thereof wherein thepolymers are endcapped by an endcapping group selected from the groupconsisting of acryloyl, methacryloyl, 2-vinylbenzyl, 3-vinylbenzyl, and4-vinylbenzyl, wherein the C units are hydrophobic macromonomer units,copolymerizable with the A monomer units and the B monomer units, the Cmacromonomer units having a number average molecular weight of fromabout 1,500 to about 50,000; and b.) a complexing fatty amine whereinthe fatty amine is selected from the group consisting of C₁ -C₂₂ primaryamines, C₁ -C₂₂ secondary amines and C₁ -C₂₂ tertiary amines, C₁ -C₂₂quaternary ammonium salts, C₁ -C₂₂ polyamines, alkyl substitutedheterocyclic amines selected from the group consisting of aminoethylhexadecylimidazoline, N-ethyl morpholine, and N-ethyl piperidine andmixtures thereof, salts thereof and mixtures thereof and wherein thefatty amine forms a complex with the acid functional B monomer unitswherein the weight ratio of the copolymer tote fatty amine is from about50:1 to about 1:1; and B.) a volatile, hydrophobic solvent component forthe copolymer complex having a boiling point at 1 atmosphere of about260° C. or less and a solubility parameter of about 8.5 (cal/cm³)^(1/2)or less wherein the copolymer complex is soluble or dispersible in thevolatile, hydrophobic solvent component and wherein the copolymercomplex and volatile, hydrophobic solvent component mixture has aviscosity of above about 5,000 cps.
 18. A hair care composition,comprising:I.) a hair styling and conditioning component, comprising:A.) a copolymer complex comprising:a.) a copolymer having a backboneformed from the copolymerization of repeating A monomer and B monomerunits wherein the backbone has optionally grafted to it hydrophobic Cmacromonomer units wherein the copolymer is prepared by thepolymerization combination of the following relative weight percentagesof the A, B, and C units:i) from about 10% to about 99% by weight of thecopolymer of one or more hydrophobic A monomer units selected from thegroup consisting of t-butyl acrylate, t-butyl methacrylate, t-butylstyrene, 2-ethylhexyl methacrylate and mixtures thereof, wherein the Amonomer units are copolymerizable with the B monomer and C macromonomerunits; ii) from about 1% to about 40% by weight of the copolymer of oneor more hydrophilic B monomer units selected from the group consistingof acrylic acid, methacrylic acid, N,N-dimethyl acrylamide, t-butylacrylamide, vinyl pyrrolidone, and mixtures thereof, wherein the Bmonomer units are copolymerizable with the A monomer and C macromonomerunits; and iii) from about 5% to about 40% by weight of the copolymer ofone or more C macromonomer units selected from the group of polymersconsisting of poly(n-butyl acrylate), poly(dodecyl acrylate),poly(2-ethylhexyl acrylate), poly(2-ethylbutyl acrylate), poly(n-ethylacrylate), poly(n-heptyl acrylate), poly(n-hexyl acrylate),poly(iso-butyl acrylate), poly(iso-decyl acrylate, poly(iso-propylacrylate), poly(3-methylbutyl acrylate), poly(2-methylpentyl acrylate),poly(nonyl acrylate), poly(octyl acrylate), poly(propyl acrylate), poly(2-ethylhexyl methacrylate), poly(tridecyl methacrylate), poly (hexylmethacrylate), poly(decyl methacrylate), poly(octyl methacrylate),poly(octadecyl methacrylate), poly(dodecyl methacrylate), poly(n-pentylmethacrylate), poly(isobutylene), poly(isoprene), hydrogenatedpoly(1,2-butadiene), hydrogenated poly(1,4-butadiene), hydrogenatedpoly(isoprene), poly(1,2-butadiene), poly(1-butene),poly(5-methyl-1-hexene), poly(6-methyl-1-heptene),poly(4,4-dimethyl-1-pentene), poly(iso-butyl vinyl ether),poly(4-t-butyl vinyl benzene-co-2-ethylhexyl acrylate),poly(2-ethylhexyl acrylate-co-octyl acrylamide), poly(2-ethyl vinylbenzene-co-octyl methacrylate), and mixtures thereof wherein thepolymers are endcapped by an endcapping group selected from the groupconsisting of acryloyl, methacryloyl, 2-vinylbenzyl, 3-vinylbenzyl, and4-vinylbenzyl, wherein the C units are hydrophobic macromonomer units,copolymerizable with the A monomer units and the B monomer units, the Cmacromonomer units having a number average molecular weight of fromabout 1,500 to about 50,000; and b.) a complexing fatty amine whereinthe fatty amine is selected from the group consisting of C₁ -C₂₂ primaryamines, C₁ -C₂₂ secondary amines and C₁ -C₂₂ tertiary amines, C₁ -C₂₂quaternary ammonium salts, C₁ -C₂₂ polyamines, alkyl substitutedheterocyclic amines selected from the group consisting of aminoethylhexadecylimidazoline, N-ethyl morpholine, and N-ethyl piperidine andmixtures thereof, salts thereof and mixtures thereof and wherein thefatty amine forms a complex with the acid functional B monomer unitswherein the weight ratio of the copolymer to the fatty amine is fromabout 50:1 to about 1:1; and B.) a volatile, hydrophobic solventcomponent for the copolymer complex having a boiling point at 1atmosphere of about 260° C. or less and a solubility parameter of about8.5 (cal/cm³)^(1/2) or less and wherein the copolymer complex is solubleor dispersible in the volatile, hydrophobic solvent component whereinthe copolymer complex and volatile, hydrophobic solvent componentmixture has a viscosity of above about 5,000 cps; andII.) a carrierimmiscible with the volatile hydrophobic solvent component.